CN1102194C - Improved Catalyst Structure Using Integral Heat Exchange - Google Patents

Abstract

The present invention is an improved catalyst structure and the use of the structure in highly exothermic processes such as catalytic combustion. The improved catalyst structure employs integral heat exchange in a series of longitudinally disposed adjacent reaction channels, either catalyst-coated (14) or catalyst-free (16), wherein the catalyst-coated channels (14) are of a different configuration than the catalyst-free channels (16) such that when applied in an exothermic reaction process, such as catalytic combustion, the desired reaction is enhanced in the catalytic channels (14) and substantially suppressed in the non-catalytic channels (16).

Description

Translated fromChinese

利用整体换热的改进型催化剂结构件Improved Catalyst Structure Using Integral Heat Exchange

                     发明领域Field of Invention

本发明涉及一种在一系列纵向布置的、相邻的、涂催化剂或无催化剂的通道中使用整体换热的催化剂结构件，也涉及在高放热方法中，如燃烧或部分燃烧方法，使用该催化剂结构件的一种方法。进一步说，本发明涉及一种使用整体换热的催化剂结构件，该结构件的催化和非催化通道在某些关键方面互不相同，从而优化了催化通道中的放热反应以及催化与非催化通道间的换热，同时非催化通道中不希望的放热反应被抑制。The present invention relates to a catalyst structure using integral heat transfer in a series of longitudinally arranged, adjacent, catalyst-coated or non-catalyst-free channels, and also relates to the use of One method of the catalyst structure. Further, the present invention relates to a catalyst structure using integral heat transfer in which the catalytic and non-catalytic channels of the structure differ in certain key respects to optimize exothermic reactions in the catalytic channels and catalytic and non-catalytic Heat exchange between channels, while undesired exothermic reactions in non-catalytic channels are suppressed.

                     发明背景Background of the Invention

在现代工业实践中众所周知，气体或蒸汽反应混合物与非均相催化剂接触可促进各种高放热反应进行。某些情况下，这种放热反应须在有外部冷却的催化剂结构件或容器中进行，部分是由于传热能力不足和反应需要控制在一定温度范围内。在这些情况下，考虑使用一种整体催化剂结构件是行不通的，这种结构件中，反应混合物的未反应部分为催化反应提供冷却。因为已有的催化剂结构件不能提供这样一种环境，使得希望的反应被优化，同时在不希望的反应和催化剂过热均可避免的条件下。用来反应的混合物通过换热除去反应热量。因此，若开发出的整体催化剂结构件具有改善的反应区环境和改善的反应混合物反应部分与未反应部分之间的换热关系，则此种催化剂结构件用于各种催化放热反应的适用性将明显改善。It is well known in modern industrial practice that various highly exothermic reactions are promoted by contacting gas or vapor reaction mixtures with heterogeneous catalysts. In some cases, such exothermic reactions have to be carried out in catalyst structures or vessels with external cooling, partly due to insufficient heat transfer capabilities and the need to control the reaction within a certain temperature range. In these cases, it is not feasible to consider the use of a monolithic catalyst structure in which the unreacted portion of the reaction mixture provides cooling for the catalytic reaction. Because existing catalyst structures do not provide an environment in which desired reactions are optimized while undesired reactions and catalyst overheating are avoided. The mixture used for the reaction removes the heat of reaction by heat exchange. Therefore, if the monolithic catalyst structure developed has an improved reaction zone environment and an improved heat transfer relationship between the reacted part and the unreacted part of the reaction mixture, the catalyst structure is suitable for various catalytic exothermic reactions. Sex will be significantly improved.

在整体催化剂结构件目前使用或建议使用的场合，如燃料燃烧或部分燃烧、催化处理燃烧发动机排放物，也非常需要改善它们的可操作性，拓宽目的催化转化反应能完成的条件。例如，在装有催化燃烧器的气体透平用催化燃烧除去气体透平排放的NOx排放物的情况下，透平的催化系统或结构件非常需要能适应各种操作情况。气体透平做为驱动负载的动力源，应能在一定速度和负载范围内使用，从而达到负载所需的动力输出。这就是说，燃烧器应可以在一定的空气和燃料流率范围内使用。若燃烧器系统使用某种催化剂燃烧燃料和限制排放物，则该催化剂系统必须能在宽的空气流率，燃料/空气(F/A)和压力范围内使用。Where monolithic catalyst structures are currently used or proposed for use, such as fuel combustion or partial combustion, and catalytic treatment of combustion engine emissions, there is also a great need to improve their operability and broaden the conditions under which the desired catalytic conversion reactions can be accomplished. For example, where a gas turbine equipped with a catalytic combustor uses catalytic combustion to remove NOx emissions from the gas turbine, it is highly desirable that the turbine's catalytic system or structure be adaptable to various operating conditions. As the power source for driving the load, the gas turbine should be able to be used within a certain speed and load range, so as to achieve the power output required by the load. This means that the burner should be usable within a certain range of air and fuel flow rates. If a burner system uses a catalyst to burn fuel and limit emissions, the catalyst system must be capable of operating over a wide range of air flow rates, fuel/air (F/A) and pressures.

特别是对发电透平，由于恒定频率发电需要转速恒定，空气流率在0％到100％载荷范围内应近似不变。但是，燃料流率将改变以适应载荷的需要，所以F/A是变化的。此外，若动力输出增加，压力会增加一些。这就是说，催化燃烧器是在宽的F/A范围，一定的压力范围和相对不变的质量流率情况下使用。另一方面，不定量的空气物流可绕过燃烧器或从气体透平中泄出以减少空气流率来保持较稳定的F/A。这将使催化剂在较窄的F/A范围和较宽的质量流率范围内使用。Especially for power generation turbines, since constant frequency power generation requires constant speed, the air flow rate should be approximately constant in the range of 0% to 100% load. However, the fuel flow rate will vary to suit the load, so F/A will vary. In addition, if the power output increases, the pressure will increase a little. That is to say, the catalytic burner is used in a wide F/A range, a certain pressure range and a relatively constant mass flow rate. On the other hand, a variable air flow can bypass the combustor or be vented from the gas turbine to reduce the air flow rate to maintain a more stable F/A. This will allow the catalyst to be used over a narrow F/A range and a wide range of mass flow rates.

进一步说，对变速透平或多级透平，空气流率和压力在操作范围内变化很大。这使得总质量流率和压力在燃烧器内变化很大。类似于上述发电透平的情况，空气可绕过或泄出用以控制F/A范围，并使燃烧器必须在一定的质量流率范围内使用。Further, for variable speed or multistage turbines, the air flow rate and pressure vary widely over the operating range. This causes the total mass flow rate and pressure to vary widely within the combustor. Similar to the case of power generation turbines above, air can be bypassed or bled to control the F/A range and necessitate the use of the burner within a certain range of mass flow rates.

如上描述的情况致使催化剂应设计得能在宽质量流率范围，压力范围和F/A范围中使用。The circumstances as described above lead to catalysts designed to be used in a wide range of mass flow rates, pressure ranges and F/A ranges.

一种从催化燃烧中受益的特别应用是装在汽车上降低排放物的气体透平。发动机启动后，必须运转于空载到满载之间，且在该全部范围排放物应很低。即使复合汽车设计中气体透平与蓄电单元联合运转，如蓄电池、飞轮等，发动机还是在空载与满载间运转，并能在两者间转换，这就要求应在这两种条件的质量流率和压力情况下均能运转。One particular application that would benefit from catalytic combustion is the gas turbines installed in automobiles to reduce emissions. After the engine is started, it must run between no load and full load, and emissions should be low throughout this range. Even if the gas turbine and the electric storage unit in the compound vehicle design operate jointly, such as batteries, flywheels, etc., the engine still runs between no-load and full-load, and can switch between the two, which requires the quality of these two conditions Operates at both flow rate and pressure.

本发明使用的催化剂结构件包含一系列相邻布置的、涂催化剂和无催化剂通道以供反应混合物流过，这些催化和非催化通道有共用壁，从而借助整体换热移走催化剂上产生的反应热并控制或抑制催化剂的温度。这就是说，在某一涂催化剂的通道，催化剂产生的热通过共用壁流到对面的非催化表面，消失在相邻无催化剂通道内的反应混合物流中。本发明中，催化与非催化通道的结构有一个或多个关键方面互不相同，包括流动通道的曲折度。这种不同致使在催化燃烧中，催化和均相燃烧在催化通道内加强，在非催化通道内未加强或基本上抑制，从而优化了热交换。这种独特结构的催化剂结构件完全拓宽了催化燃烧和/或部分燃烧中操作参数的范围。The catalyst structure used in the present invention comprises a series of adjacently arranged, catalyst-coated and catalyst-free channels through which the reaction mixture flows, the catalytic and non-catalytic channels have common walls, thereby removing the reactions occurring on the catalyst by means of bulk heat transfer. heat and control or suppress the temperature of the catalyst. That is, in one catalyst-coated channel, the heat generated by the catalyst flows through the common wall to the opposite non-catalytic surface and is lost in the flow of the reaction mixture in the adjacent catalyst-free channel. In the present invention, the structures of catalytic and non-catalytic channels differ in one or more key aspects, including the tortuosity of the flow channels. This difference is such that in catalytic combustion, catalytic and homogeneous combustion is enhanced in catalytic channels and not enhanced or substantially suppressed in non-catalytic channels, thereby optimizing heat exchange. This unique configuration of the catalyst structure completely broadens the range of operating parameters in catalytic combustion and/or partial combustion.

在催化促进燃烧或部分燃烧中使用整体换热催化剂支撑件是众所周知的，Japanese Kokai 59-136,140(1984年8月4日公开)和Kokai 61-259,013(1986年11月17日公开)公开了使用整体换热的技术，其中一种是方形载面陶瓷整体催化剂支撑件，支撑件中交替的纵向通道(或层)上沉积有催化剂，另一种是由同心圆柱组成的支撑件结构，支撑件内交替的环状空间涂有催化剂。在此两种情况中，公开的催化剂结构件设计是：涂催化剂和无催化剂通道的结构与催化和非催化流动通道相同，每种通道基本上是直的并在其全长度上截面积相同。The use of integral heat exchange catalyst supports in catalytically promoted combustion or partial combustion is well known, Japanese Kokai 59-136,140 (published August 4, 1984) and Kokai 61-259,013 (published November 17, 1986) disclose the use of Integral heat exchange technology, one of which is a square-faced ceramic monolithic catalyst support, in which alternate longitudinal channels (or layers) are deposited with catalysts, and the other is a support structure composed of concentric cylinders, the support The inner alternating annulus are coated with catalyst. In both cases, the disclosed catalyst structure design is such that the catalyst-coated and non-catalyzed channels are identical in structure to the catalytic and non-catalytic flow channels, each channel being substantially straight and having the same cross-sectional area throughout its length.

与两个Japanese Kokai非常相似的公开专利是Young等人的美国专利4,870,824，该专利使用的整体换热是在一种蜂窝型支撑件结构，其中涂布和无催化剂通道具有相同的结构，并且基本是直的和沿其全长度上截面积相同。A published patent very similar to the two Japanese Kokai is U.S. Patent 4,870,824 to Young et al, which uses integral heat transfer in a honeycomb-type support structure in which the coated and catalyst-free channels have the same structure and essentially is straight and has the same cross-sectional area along its entire length.

近来，一系列美国专利，包括美国专利5,183,401；5,232,357；5,248,251；5,250,489和5,259,754授权给Dalla Betta等人。这些专利描述了在各种燃烧或部分燃烧方法或系统中使用的整体换热，包括在整体换热催化剂结构件上进行燃料部分燃烧后再在催化剂后进行完全燃烧的过程。在这些专利中，美国专利5,250,489最接近本发明，该专利涉及一种金属催化剂支撑件，该支撑件是由耐高温金属制成的，该金属形成用于通过可燃气的一系列纵向通道。支撑件内，涂催化剂通道催化表面上的热是由至少部分涂催化剂的通道与无催化剂通道间进行的整体换热移走。US 5,250,489公开的催化剂支撑结构件包括结构件(US 5,250,489的图6A和6B)其中可燃气通道或孔道是由波纹金属板的交替的宽、窄波纹形成的，交替的催化和非催化通道的尺寸是变化的，使得在一种情况下80％的气体流过催化通道，20％的气体流过非催化通道(图6A)，另一种情况下20％的气体流过催化通道而80％的气体流过非催化通道(图6B)。利用不同尺寸的通道作为设计规范，该专利表明：借助整体换热，可燃气转化成燃烧产物转化率可达到5％到95％间任何值。虽然该专利公开了利用不同转化率的催化和非催化通道来改变转化率，但它明显未考虑在催化与非催化通道间利用不同的通道曲折度来优化催化通道中的燃烧反应，基本上限制非催化通道中的均相燃烧做为一种手段用来拓宽催化剂结构件能有效操作的工艺条件。Recently, a series of US patents including US Patents 5,183,401; 5,232,357; 5,248,251; 5,250,489 and 5,259,754 were issued to Dalla Betta et al. These patents describe the use of integral heat exchange in various combustion or partial combustion methods or systems involving partial combustion of fuel on an integral heat exchange catalyst structure followed by complete combustion behind the catalyst. Of these patents, the closest to the present invention is US Patent 5,250,489, which relates to a metal catalyst support made of a refractory metal forming a series of longitudinal channels for the passage of combustible gases. Within the support, heat is removed from the catalytic surfaces of the catalyst-coated channels by bulk heat exchange between the at least partially catalyst-coated channels and the non-catalyst channels. Catalyst support structures disclosed in US 5,250,489 include structures (Figures 6A and 6B of US 5,250,489) in which combustible gas passages or channels are formed by alternating wide and narrow corrugations of corrugated metal sheets, the dimensions of the alternating catalytic and non-catalytic passages is varied so that in onecase 80% of the gas flows through the catalytic channel, 20% of the gas flows through the non-catalytic channel (Figure 6A), in another case 20% of the gas flows through the catalytic channel and 80% of the gas Gas flows through non-catalytic channels (Figure 6B). Using channels of different sizes as design criteria, the patent shows that the conversion of combustible gas to combustion products can reach any value between 5% and 95% by means of integral heat exchange. Although this patent discloses the use of catalytic and non-catalytic channels with different conversion rates to change the conversion rate, it obviously does not consider the use of different channel tortuosity between the catalytic and non-catalytic channels to optimize the combustion reaction in the catalytic channel, basically limiting Homogeneous combustion in non-catalytic channels is used as a means to broaden the process conditions under which catalyst structures can operate effectively.

在整体换热结构件用来进行燃料部分燃烧后再进行催化剂后完全燃烧的情况下，催化剂燃烧部分燃料并产生足够热的出口气来引发催化剂后的均相燃烧。另外，催化剂不能变得太热，因为这将缩短催化剂寿命并抑制该方法的优点。若改变催化剂使用条件，注意到用以上描述的先有技术的整体换热结构件，这类催化剂的操作范围被限制。这就是说，为防止过热，气速或质量流率仅能处于一定的范围以内。Where the integral heat exchange structure is used for partial combustion of the fuel followed by complete post-catalyst combustion, the catalyst combusts a portion of the fuel and produces an outlet gas hot enough to initiate homogeneous post-catalyst combustion. Also, the catalyst must not become too hot as this would shorten catalyst life and inhibit the benefits of the process. If the catalyst use conditions are changed, it is noted that with the prior art monolithic heat exchange structure described above, the operating range of this type of catalyst is limited. That is, to prevent overheating, the gas velocity or mass flow rate can only be within a certain range.

因此，明显需要改进使用整体换热的催化剂结构件，该结构件能大大拓宽这类催化结构件可用在高放热过程中(如催化燃烧或部分燃烧)的操作条件范围或区域。本发明是在一种整体换热结构件中使用了一些关键性的不同的催化通道结构和非催化通道结构，从而大大地拓宽了该催化剂的使用范围。Accordingly, there is a clear need for improved catalytic structures utilizing integral heat transfer that greatly broaden the range or region of operating conditions over which such catalytic structures can be used in highly exothermic processes such as catalytic combustion or partial combustion. The present invention uses some key different catalytic channel structures and non-catalytic channel structures in an integral heat exchange structure, thereby greatly broadening the application range of the catalyst.

                     发明综述Summary of Invention

广义地讲，本发明提供一种新型的催化剂结构件，该结构件包括一系列相邻布置的用于流过反应混合物的涂催化剂和无催化剂通道，这些通道中，至少部分涂催化剂的通道与相邻的无催化剂通道形成换热关系，而且涂催化剂的通道比无催化剂通道具有更曲折的流动路径。为方便起见，本文术语“涂催化剂通道”或“催化通道”在本发明催化剂结构件中可涉及单个通道或一组相邻的通道，且催化剂涂布了它们的至少部分表面。事实上，一个较大的催化通道可被催化剂支撑壁或可渗透和不可渗透的阻挡物划分成一系列较小的通道，这些阻挡物可能涂布或未涂布催化剂。类似地，“无催化剂通道”或“非催化通道”可以是完全未涂催化剂的单个通道或一组相邻的通道。这就是说，较大的无催化剂通道可被无催化剂的支撑壁或未涂催化剂的可渗透和不可渗透的阻碍物划分为一系列较小的通道。据此，增加涂催化剂通道的曲折度意味着涂催化剂通道被设计成：流入该涂催化剂通道的至少一部分反应混合物，当其流过整个通道时，其流动方向比进入无催化剂通道中的任何类似部分反应混合物变化更多。若假设涂催化剂通道进口与出口间的纵轴是直线，增加此通道的曲折度将使反应混合物流动路径与轴之间的偏差变大，因此沿此种偏差的运动轨迹长于沿轴的运动轨迹。Broadly speaking, the present invention provides a novel catalyst structure comprising a series of adjacently arranged catalyst-coated and catalyst-free channels for flowing a reaction mixture, wherein the at least partially catalyst-coated channels are in contact with Adjacent uncatalyzed channels form a heat exchange relationship, and the catalyst-coated channels have a more tortuous flow path than the uncatalyzed channels. For convenience, the term "catalyst-coated channel" or "catalytic channel" herein in the catalyst structure of the present invention may refer to a single channel or a group of adjacent channels having at least a portion of their surface coated with catalyst. In fact, a larger catalytic channel can be divided into a series of smaller channels by catalyst support walls or permeable and impermeable barriers, which may or may not be coated with catalyst. Similarly, a "catalyst-free channel" or "non-catalytic channel" may be a single channel or a group of adjacent channels that are completely uncoated with catalyst. That is, larger catalyst-free channels can be divided into a series of smaller channels by catalyst-free support walls or uncatalyzed permeable and impermeable barriers. Accordingly, increasing the tortuosity of a catalyst-coated channel means that a catalyst-coated channel is designed such that at least a portion of the reaction mixture flowing into the catalyst-coated channel flows in a direction that is more direct than any similar reaction mixture entering a catalyst-free channel as it flows through the entire channel. Some reaction mixtures vary more. Assuming that the longitudinal axis between the inlet and outlet of the catalyst-coated channel is a straight line, increasing the tortuosity of this channel will cause the deviation between the flow path of the reaction mixture and the axis to become larger, so that the trajectory along this deviation is longer than that along the axis .

在实际中，增加涂催化剂通道中流动通道的曲折度可通过对通道作各种结构改进来完成。它包括沿其纵轴周期性地改变通道的方向和/或截面积，同时保持无催化剂通道完全是直线和不变的截面积。较好的，增大涂催化剂通道的曲折度通过改变其截面积来完成，这可通过沿通道纵轴重复地向内和向外弯曲通道壁或者在通道纵轴方向的许多地方插入挡极、折流板或其它阻挡物以部分阻挡和/或改变反应混合物在通道中的流动方向。In practice, increasing the tortuosity of the flow channels in the catalyst-coated channels can be accomplished by making various structural modifications to the channels. It consists of periodically changing the direction and/or cross-sectional area of the channels along their longitudinal axis while keeping the catalyst-free channels perfectly straight and of constant cross-sectional area. Preferably, increasing the tortuosity of the catalyst-coated channel is accomplished by changing its cross-sectional area, which can be accomplished by repeatedly bending the channel wall inwards and outwards along the longitudinal axis of the channel or by inserting barriers, Baffles or other barriers to partially block and/or redirect the flow of the reaction mixture in the channels.

一个较好的方面，本发明催化剂结构件的进一步特征是：涂催化剂通道在一个或若干个关键结构单元上与无催化剂通道不同，这些单元本身又利用和延伸了增加涂催化剂通道曲折度的概念。具体地说，本发明催化剂结构件独特地使用了一系列至少部分内表面涂有催化剂的纵向分布通道，即与相邻无催化剂通道形成换热关系的涂催化剂通道，其中：In a better aspect, the further feature of the catalyst structure of the present invention is: the catalyst-coated channel is different from the catalyst-free channel on one or several key structural units, and these units themselves utilize and extend the concept of increasing the tortuosity of the catalyst-coated channel . Specifically, the catalyst structure of the present invention uniquely utilizes a series of longitudinally distributed channels having at least a portion of their interior surfaces coated with catalyst, i.e., catalyst-coated channels in heat exchange relationship with adjacent non-catalyzed channels, wherein:

(a)涂催化剂通道较无催化剂通道具有较小的平均水力学直径(D_h)，并且/或；(a) the catalyst-coated channels have a smaller mean hydraulic diameter (D_h ) than the catalyst-free channels, and/or;

(b)涂催化剂通道较无催化剂通道具有较高的膜传热系数(h)。平均水力学直径(D_h)被定义为：催化剂结构件中某类通道(如涂催化剂通道)的平均截面积乘以4再除以同一结构件，同一类型通道的平均润湿周长。由此D_h发现，无催化剂通道最好设计为具有较大的水力学直径，并且比催化通道受结构的改变影响要小。膜传热系数(h)是一个实验确定的值。它关联和表达了催化剂结构件中涂盖催化剂通道的平均曲折度与无催化剂通道的平均曲折度之比。(b) The catalyst-coated channel has a higher membrane heat transfer coefficient (h) than the catalyst-free channel. The average hydraulic diameter (D_h ) is defined as: the average cross-sectional area of a certain type of channel (such as a catalyst-coated channel) in a catalyst structure multiplied by 4 and then divided by the average wetted perimeter of the same type of channel in the same structure. From this D_h found that catalyst-free channels are best designed with larger hydraulic diameters and are less affected by structural changes than catalytic channels. The film heat transfer coefficient (h) is an experimentally determined value. It correlates and expresses the ratio of the average tortuosity of the catalyst-coated channels to the average tortuosity of the catalyst-free channels in the catalyst structure.

如果除了控制上面所述的平均D_h和/或h，还控制涂催化剂和无催化剂通道之间的传热表面积，使得此表面积与总通道的体积之比大于0.5mm^-1，则本发明催化剂结构件可被进一步优化。If, in addition to controlling the above-mentioned average D_h and/or h, the heat transfer surface area between the catalyst-coated and catalyst-free channels is controlled such that the ratio of this surface area to the volume of the total channels is greater than 0.5 mm^-1 , the catalyst of the present invention Structural elements can be further optimized.

本发明催化剂结构件装有适当的催化材料特别适用于燃烧或部分燃烧过程，其中气体或蒸汽形式的燃料通常在催化剂结构件上部分燃烧后，再在催化剂下游完全燃烧。利用本发明催化剂结构件比至今已有的先有技术的催化剂结构件(包括使用整体换热的结构件)在较宽的线速度、气体进口温度和压力范围内可在催化剂通道内获得更加完全的燃烧，同时在非催化剂通道内进行最少的燃烧。因此，本发明包括了一种用于可燃燃料燃烧或部分燃烧的改进型催化剂结构件，也包括了一种使用本发明催化剂结构件燃烧可燃烧料和空气或含氧气体的混合物的燃烧方法。Catalyst structures according to the invention equipped with suitable catalytic materials are particularly suitable for combustion or partial combustion processes in which the fuel in gas or vapor form is usually partially combusted on the catalyst structure and then completely combusted downstream of the catalyst. Utilizing the catalyst structure of the present invention can achieve more completeness in the catalyst channel over a wider range of linear velocity, gas inlet temperature and pressure than the prior art catalyst structure (including the structure using integral heat exchange) so far. combustion with minimal combustion in the non-catalyst channels. Accordingly, the present invention includes an improved catalyst structure for the combustion or partial combustion of combustible fuels, as well as a method of combusting a mixture of a combustible material and air or an oxygen-containing gas using the catalyst structure of the invention.

                  附图的简要说明A brief description of the drawings

图1，2，3，3A，3B和3C示意地描绘了先有技术的结构，示出了使用整体换热催化剂结构件的常见形式。Figures 1, 2, 3, 3A, 3B and 3C schematically depict prior art structures showing common forms of structure using integral heat exchange catalysts.

图4，5，6，7和8显示了本发明结构件的各种结构。Figures 4, 5, 6, 7 and 8 show various configurations of the structural member of the present invention.

                     发明说明Description of Invention

当应用于高放热反应催化过程中，本发明催化剂结构件通常是整体型结构件，该结构件包括一种由多个共用壁组成的耐热支撑件材料，这些壁形成一系列相邻布置的纵向通道以供一种流动的气体反应混合物流过，其中至少一部分通道在它们的内表面的至少一部分涂有用于反应混合物的催化剂(涂催化剂通道)，余下的通道在它们的内表面不涂催化剂(无催化剂通道)，这样涂催化剂通道的内表面与相邻的无催化剂的通道的内表面形成热交换关系，和其中涂催化剂通道在结构上与无催化剂通道不同，这导致目的反应在催化剂通道内促进而在非催化通道内被抑制。当本发明结构件用于催化燃烧或部分燃烧过程，催化与非催化通道间在设计上的关键差异是确保在较宽的线速度，进口气体温度和压力范围催化通道内燃烧更完全而非催化通道内仅有最少的燃烧。When used in catalytic processes for highly exothermic reactions, catalyst structures of the present invention are typically monolithic structures comprising a refractory support material consisting of a plurality of shared walls forming a series of adjacent arrangements Longitudinal channels for a flowing gaseous reaction mixture to flow through, wherein at least some of the channels are coated with catalyst for the reaction mixture on at least a part of their inner surfaces (catalyst-coated channels), and the remaining channels are not coated on their inner surfaces catalyst (catalyst-free channels), such that the inner surface of the catalyst-coated channel is in heat exchange relationship with the inner surface of an adjacent catalyst-free channel, and wherein the catalyst-coated channel is structurally different from the catalyst-free channel, which results in the desired reaction in the catalyst Promoted in the channel and inhibited in the non-catalyzed channel. When the structure of the present invention is used for catalytic combustion or partial combustion processes, the key difference in design between catalytic and non-catalytic channels is to ensure more complete combustion in catalytic channels rather than catalytic over a wide range of linear velocity, inlet gas temperature and pressure. There is only minimal combustion in the channel.

本发明催化结构件的催化与非催化通道间在设计上的关键差异基本上是：催化通道应设计成由催化通道限定的反应混合物流动路径比由非催化通道限定的相应的流动路径有较高或增大的曲折度。此处所用的曲折度的概念被定义为给定部分反应混合物流过在流动方向和/或通道横截面积有变化的通道流经的路径长度与类似部分的反应混合物流过同样总长度而在方向或横截面积均无变化的通道(即横截面无变化的直通道)流经的路径长度之差。与直线路径的偏离导致了更长或更大的曲折路径，并且与直线路径的偏离越大，流经路径越长。对于本发明催化剂结构件，催化与非催化通道间曲折度的差异是通过比较结构件中所有催化通道的平均曲折度与所有非催化通道的平均曲折度确定的。The key difference in design between the catalytic and non-catalytic channels of the catalytic structure of the present invention is basically that the catalytic channels should be designed such that the reaction mixture flow paths defined by the catalytic channels have a higher flow path than the corresponding flow paths defined by the non-catalytic channels. or increased tortuosity. The concept of tortuosity as used herein is defined as the path length of a given portion of the reaction mixture flowing through a channel that varies in flow direction and/or channel cross-sectional area compared to a similar portion of the reaction mixture flowing through the same total length at The difference in the path lengths of passages that have no change in direction or cross-sectional area (that is, straight channels with no change in cross-section). Deviations from a straight path result in longer or more tortuous paths, and the greater the deviation from a straight path, the longer the flow path. For catalyst structures of the present invention, the difference in tortuosity between catalytic and non-catalytic channels is determined by comparing the average tortuosity of all catalytic channels in the structure to the average tortuosity of all non-catalytic channels.

在本发明催化剂结构件中，对涂催化剂的通道可进行许多结构改型以增加其相对于非催化通道的曲折度。具体地说，增大催化通道的曲折度可通过周期性地改变通道的方向，例如，使用锯齿形或波纹形通道，或借助沿其纵轴方向周期性地向内和向外弯曲通道壁或者是在通道纵轴的一系列位置上插入的挡板、折流板或其它阻挡物以部分地阻挡或改变反应混合物流流动方向来重复地改变通道横截面积。在某些应用中，需要使用方向和截面积的联合变化以达到最优曲折度差值，但是在所有情况下，非催化通道的曲折度在平均值上小于催化通道的曲折度。In the catalyst structures of the present invention, a number of structural modifications can be made to the catalyst-coated channels to increase their tortuosity relative to the non-catalyzed channels. Specifically, the tortuosity of the catalytic channels can be increased by periodically changing the direction of the channels, for example, using zigzag or corrugated channels, or by periodically bending the channel walls inward and outward along their longitudinal axis or Baffles, baffles, or other barriers inserted at a series of locations along the longitudinal axis of a channel to partially block or redirect the flow of the reaction mixture to repeatedly vary the channel cross-sectional area. In some applications, it is necessary to use a combination of orientation and cross-sectional area to achieve the optimal tortuosity difference, but in all cases the tortuosity of the non-catalytic channels is on average less than that of the catalytic channels.

较好地，催化通道曲折度的增大是用通过改变其纵轴上一系列位置的截面积来完成。对催化通道，一种较好地实现改变曲折度的方法(下面将进一步详细说明)包括使用非嵌套叠置排列的波纹板催化剂支撑件材料。这些波纹板是人字型波纹，并且某一波纹板的一边的至少一部分面对和叠置在另一个涂有催化剂的波纹板上。因此上述叠置板形成了一系列催化通道。借助以非嵌套方式叠置在一起的波纹板，叠置板形成的通道在纵轴方向交替地扩张和收缩其截面积，这是由人字形波纹片向内和向外弯曲形成的波峰和波谷造成的。改变涂催化剂通道截面积的另一种较好的方式包括沿纵轴方向周期性地在通道两侧交替地放置挡板或折流板，或者在催化通道的流动路径上使用隔板或其它阻挡物。为避免不必要的经过通道的压力降，放置在通道流动路径上的阻挡物不应当使通道横截面积的减少超过其总横截面积的40％。Preferably, the increase in the tortuosity of the catalytic channel is accomplished by varying its cross-sectional area at a series of positions along its longitudinal axis. A preferred method of achieving varying tortuosity for catalytic channels (described in further detail below) involves the use of corrugated sheets of catalyst support material in a non-nested stacked arrangement. These corrugated plates are herringbone corrugated, and at least a part of one side of a certain corrugated plate faces and overlaps another catalyst-coated corrugated plate. The above stacked plates thus form a series of catalytic channels. With the corrugated plates stacked together in a non-nesting manner, the channel formed by the stacked plates expands and contracts its cross-sectional area alternately in the direction of the longitudinal axis, which is the crest and caused by troughs. Another preferred way to change the cross-sectional area of the catalyst-coated channel includes periodically placing baffles or baffles alternately on both sides of the channel along the longitudinal axis, or using baffles or other barriers in the flow path of the catalytic channel. things. To avoid unnecessary pressure drop across the channel, obstructions placed in the channel flow path should not reduce the cross-sectional area of the channel by more than 40% of its total cross-sectional area.

如前所述，在本发明优选的催化剂结构件中，涂催化剂通道不同于无催化剂通道是它的平均水力学直径(D_h)小于无催化剂通道，和/或它的膜传热系数(h)大于无催化剂通道的。更优选，涂催化剂通道与无催化剂通道相比既有较低的D_h也有较高的h。As previously mentioned, in the preferred catalyst structure of the present invention, the catalyst-coated channel differs from the catalyst-free channel in that its average hydraulic diameter (D_h ) is smaller than that of the catalyst-free channel, and/or its membrane heat transfer coefficient (h ) is larger than that of the catalyst-free channel. More preferably, the catalyst-coated channels have both a lower Dh and a higher_h than the catalyst-free channels.

平均水力学直径在Whitaker，Fundamental Principles of HeatTransfer，Krieger Publishing Company(1983)中第296页，用下列表达式定义：The mean hydraulic diameter is defined in Whitaker, Fundamental Principles of Heat Transfer, page 296, Krieger Publishing Company (1983), by the following expression:

              D_h＝4[横截面积/润湿周长]D_h = 4 [cross-sectional area / wetted perimeter]

这样，对本发明催化剂结构件，平均D_h可通过逐一计算每个通道沿其整个长度的平均D_h而求出结构件中所有涂催化剂通道的平均D_h，然后将计算的每个通道的D_h乘以代表该通道前开口面积分率的权因子，再加和得到涂催化剂通道的平均D_h。按同样的方法，可确定结构件中无催化剂通道的平均D_h。Like this, to the catalyst structure of the present invention, the average D_h can obtain the average D_{h of all coated catalyst channels in the structure by calculating the average D hof} each channel along its entire length one by one, and then the D of each channel calculated_h is multiplied by a weighting factor representing the fraction of open frontal area of the channel, and summed to obtain the average D_h of the catalyst-coated channel. In the same way, the average_Dh of the catalyst-free channels in the structure can be determined.

如上所述，涂催化剂通道最好比无催化剂通道具有较小的平均D_h能部分地被解释成涂催化剂通道的表面积与体积比最好高于无催化剂通道的，因为水力学直径与表面积体积比成反比例关系。进一步说，在本发明催化剂结构件中，涂催化剂通道和无催化剂通道的平均D_h差异意味着一般无催化剂通道是更开放的通道，因此，改变其通道直径对气体流动的影响比在涂催化剂通道中小。部分是由于涂催化剂通道中表面积与体积比较高。较好地，涂催化剂通道与无催化剂通道的平均D_h的数值比例，也就是涂催化剂通道的平均D_h除以无催化剂通道的平均D_h是在0.15到0.9之间。更好地，涂催化剂通道与无催化剂通道的平均D_h之比是在0.3到0.8之间。As mentioned above, catalyst-coated channels preferably have a smaller average_Dh than uncatalyzed channels can partly be explained by the fact that catalyst-coated channels preferably have a higher surface area-to-volume ratio than uncatalyzed channels because the hydraulic diameter versus surface area-to-volume ratio is inversely proportional. Further, in the catalyst structures of the present invention, the difference in average D_h between catalyst-coated and non-catalyst channels means that in general non-catalyst channels are more open channels, and therefore, changing their channel diameters has a greater effect on gas flow than catalyst-coated channels. The channel is small and medium. This is partly due to the high surface area to volume ratio in the catalyst-coated channels. Preferably, the numerical ratio of the average D_h of the catalyst-coated channels to the catalyst-free channels, ie the average D_h of the catalyst-coated channels divided by the average D_h of the catalyst-free channels, is between 0.15 and 0.9. More preferably, the average_Dh ratio of the catalyst-coated channels to the catalyst-free channels is between 0.3 and 0.8.

膜传热系数h是无单位数值，是通过下列步骤实验测定的：气体，即空气或空气/燃料混合物，在给定入口温度下，流过一个具有特定通道结构和温度的适当试验结构件，并测量出口气体温度，h可由实验测定的数值用下面的方程式计算。该方程式用路径增量Δx来描述传热(见Whitaker，lbid.第13页和14页，方程式1.3-29和1.3-31。The film heat transfer coefficient h is a unitless value and is determined experimentally by the following steps: a gas, i.e. air or an air/fuel mixture, flows through an appropriate test structure with a specific channel configuration and temperature at a given inlet temperature, And measure the outlet gas temperature, h can be calculated from the experimentally determined value with the following equation. This equation describes heat transfer in terms of path increment Δx (see Whitaker, lbid.pages 13 and 14, equations 1.3-29 and 1.3-31.

FCp(ΔTgas)＝hA(Twall-Tgas)ΔxFCp(ΔTgas)=hA(Twall-Tgas)Δx

其中：in:

F是气体流率；F is the gas flow rate;

Cp是气体热容；Cp is the heat capacity of the gas;

h是传热系数；h is the heat transfer coefficient;

A是单位通道长度的壁面积；A is the wall area per unit channel length;

ΔTgas是经过距离增量Δx的气体物流中的温升；ΔTgas is the temperature rise in the gas stream over a distance increment Δx;

Twall是位置x处的壁温度；Twall is the wall temperature at position x;

Tgas是位置x处气体温度。Tgas is the gas temperature at position x.

从该实验结构件的入口到出口积分此方程式可确定膜传热系数h，该系数给出一个与实验吻合的计算出口气体温度。Integrating this equation from the inlet to the outlet of the experimental structure determines the film heat transfer coefficient h which gives a calculated outlet gas temperature which is in good agreement with the experiment.

在本发明催化剂结构件中，因为在催化和非催化通道中的气体组成、流率、压力和温度非常相似，膜传热系数提供了有效表征不同流动形状的手段，该流动形状是由各种流动通道结构确定的，该结构可区别本发明催化剂结构件中的涂催化剂通道和无催化剂通道。In the catalyst structure of the present invention, because the gas composition, flow rate, pressure and temperature in the catalytic and non-catalytic channels are very similar, the film heat transfer coefficient provides a means to effectively characterize the different flow shapes, which are determined by various The flow channel structure is determined, and the structure can distinguish the catalyst-coated channel and the catalyst-free channel in the catalyst structure of the present invention.

因为这些不同的流动形状本身是又与通道形成的流动路径的曲折度有关，膜传热系数用于本发明催化剂结构件中提供了曲折度的测量方法。本领域技术人员可设计出各种方法测定或确定本发明催化剂结构件的h。一种简便的方法可包括制备一个实验检测结构件，例如一个固体厚金属结构件，通过机械加工其内部空间摸拟目的通道的形状，然后在下列情况下进行测试，其中壁温可以是从入口到出口间基本恒定或者变化，并沿此结构件中通道长度的若干点上测量壁温度。对图1描述的直线通道整体结构件(见下面讨论)，试验结构件可以是一个通道或一组线性排列的通道。对如图2所示的人字型波纹整体件(也见下面讨论)，试验结构件可以是含有非嵌套人字型结构通道的线性区域的一部分，这种通道是处在两个足够宽以将壁效应降至最低的金属板之间。Because these different flow shapes are themselves related to the tortuosity of the flow path formed by the channels, the use of the membrane heat transfer coefficient in the catalyst structure of the present invention provides a measure of the tortuosity. Those skilled in the art can devise various methods for determining or determining h for the catalyst structures of the present invention. A convenient method may include preparing an experimental test structure, such as a solid thick metal structure, by machining its internal space to simulate the shape of the desired channel, and then testing under the following conditions, where the wall temperature can be from the inlet The wall temperature is measured at several points along the length of the channel in the structure, either substantially constant or varying to the outlet. For the rectilinear channel monolithic structure depicted in Figure 1 (see discussion below), the test structure may be a channel or a set of channels in a linear arrangement. For a corrugated chevron monolith as shown in Figure 2 (see also discussion below), the test structure may be part of a linear region containing channels of non-nested chevron structures between two sufficiently wide between metal plates to minimize wall effects.

通过制备所需要的实验结构件如上所述的技术可用于本文描述的任何一种结构件。在催化剂结构件是由几种不同通道结构组分的情况下，每种通道结构可分别测试，并且h(cat)/h(non-cat)数值比是通过对结构件中每种通道类型的h(乘以表示前开口面积分率的权因子)求和，然后用催化通道的h和除以非催化通道的h和确定的。The techniques described above can be used for any of the structures described herein by preparing the required experimental structures. In the case where the catalyst structure is composed of several different channel structures, each channel structure can be tested separately, and the numerical ratio of h(cat)/h(non-cat) is calculated for each channel type in the structure h (multiplied by a weighting factor representing the fraction of the front opening area) is summed and then determined by dividing the h sum of the catalytic channel by the h sum of the non-catalytic channel.

用来表征本发明催化剂结构件中涂催化剂和无催化剂通道结构差异的h(cat)/h(non-cat)比值可进一步定义为：在h(cat)/h(non-cat)大于1的情况下，涂催化剂通道以平均水力学直径(D_h)除以无催化剂通道的平均水力学直径(Dh)的数值比小于涂催化剂通道的前开口面积除以无催化剂通道的前开口面积的数值比。此处所用的前开口面积指某给定类型(即催化或非催化)通道在所述催化剂结构件中的平均截面积；该截面积是对通道中反应混合物流开放的区域，在垂直反应混合物流方向上测量的截面积。引入此种基于前开口面积的数值比反映出的事实是：本发明涂催化剂通道较无催化剂通道有足够大的曲折度差值以明显地区别于已有技术中使用整体换热的结构件，在已有技术结构件中，流过催化和非催化通道的流体比值是由使用同样结构的不同通道大小来控制的。这就是说，在已有技术结构件中，若少于50％的反应混合物流通过催化通道，则催化通道的平均D_h小于非催化通道的，并且h(cat)/h(non-cat)的比值超过1。通过引入催化通道平均D_h除以非催化通道平均D_h的比值必须小于催化通道前开口面积除以非催化通道前开口面积的比值这一概念，这样本发明催化剂结构件能明显区别于已有技术结构件。The h(cat)/h(non-cat) ratio that is used to characterize the difference in the structure of the catalyst structure of the present invention to be coated with the catalyst and the non-catalyst channel can be further defined as: when h(cat)/h(non-cat) is greater than 1 In some cases, the numerical ratio of the average hydraulic diameter (D_h ) of the catalyst-coated channel divided by the average hydraulic diameter (Dh) of the catalyst-free channel is smaller than the value of the front opening area of the catalyst-coated channel divided by the front opening area of the catalyst-free channel Compare. Front opening area as used herein refers to the average cross-sectional area of a given type of (i.e., catalytic or non-catalytic) channel in the catalyst structure; this cross-sectional area is the area open to the flow of the reaction mixture in the channel, which The cross-sectional area measured in the flow direction. The introduction of this numerical ratio based on the area of the front opening reflects the fact that the catalyst-coated channel of the present invention has a large enough tortuosity difference compared with the catalyst-free channel to clearly distinguish it from structural members using integral heat transfer in the prior art, In prior art structures, the ratio of fluid flow through catalytic and non-catalytic channels was controlled by using different channel sizes of the same structure. That is, in prior art structures, if less than 50% of the reaction mixture flows through the catalytic channels, the average D_h of the catalytic channels is less than that of the non-catalytic channels, and h(cat)/h(non-cat) ratio exceeds 1. By introducing the concept that the ratio of the average D_h of the catalytic channel divided by the average D_h of the non-catalytic channel must be less than the ratio of the area of the front opening of the catalytic channel to the area of the front opening of the non-catalytic channel, the catalyst structure of the present invention can be clearly distinguished from existing ones. Technical structural parts.

另一方面，本发明催化剂结构件区别于已有技术结构件的特征是使用了高于已有技术的催化与非催化通道间的传热膜系数(h)比，已有技术结构件是指使用大小不同而结构相同的催化和非催化通道的结构件。在已有技术直线通道结构件中，催化通道占有20％的前开口面积，非催化通道占有80％的前开口面积，催化通道的传热系数是非催化通道的1.5倍左右。本发明结构件中，催化通道的传热系数与非催化通道的传热系数比值远远大于1.5倍。更确切地说，对于在催化和非催化通道间有各种反应物流动分布情况的催化剂结构件，下表定义了本发明催化剂结构件。 总反应混合物中通过催化通道的百分比h(cat)/h(non-cat)     ≥50     ＞1.0     大于40小于50     ＞1.2     大于30小于40     ＞1.3     大于20小于30     ＞1.5     大于10小于20     ＞2.0在任何情况中，若h(cat)/h(non-cat)的比值大于1，这就意味着，涂催化剂通道的h大于无催化剂通道的，则此催化剂结构件在本发明范围内。较好地，本发明催化剂结构件的h(cat)/h(non-cat)比值在1.1到7之间，更好地，此比值在1.3到4之间。On the other hand, the catalyst structure of the present invention differs from the prior art structure in that it uses a ratio of the heat transfer film coefficient (h) between the catalytic and non-catalytic passages that is higher than that of the prior art. The prior art structure refers to Structures using catalytic and non-catalytic channels of different sizes but identical structure. In the prior art linear channel structure, the catalytic channel occupies 20% of the front opening area, and the non-catalytic channel occupies 80% of the front opening area. The heat transfer coefficient of the catalytic channel is about 1.5 times that of the non-catalytic channel. In the structural part of the present invention, the ratio of the heat transfer coefficient of the catalytic channel to the heat transfer coefficient of the non-catalytic channel is far greater than 1.5 times. More specifically, the following table defines the catalyst structures of the present invention for catalyst structures having various reactant flow profiles between catalytic and non-catalytic channels. Percentage of total reaction mixture that passes through catalytic channels h(cat)/h(non-cat) ≥50 >1.0 Greater than 40 and less than 50 >1.2 Greater than 30 and less than 40 >1.3 greater than 20 less than 30 >1.5 greater than 10 less than 20 >2.0 In any event, if the ratio h(cat)/h(non-cat) is greater than 1, meaning that h is greater for catalyst-coated channels than for non-catalyst channels, the catalyst structure is within the scope of the invention. Preferably, the h(cat)/h(non-cat) ratio of the catalyst structure of the present invention is between 1.1 and 7, more preferably, the ratio is between 1.3 and 4.

如前所述，若涂催化剂和无催化剂孔道被设计成涂催化剂通道和无催化剂通道之间的传热表面积除以催化剂结构件中全部通道体积大于0.5mm^-1，本发明催化剂结构件的性能可进一步被优化。较好地，在本发明结构件中，催化通道和非催化通道之间的传热面积除以催化剂结构件总通道体积的比值R是在0.5mm^-1到2mm^-1之间，更好地，R值在0.5mm^-1到1.5mm^-1之间。利用传热表面对总体积的高比值R，优化了从通道壁上催化剂一边到非催化一边并扩散到流动反应混合物中的传热。由于利用整体换热优化了催化剂表面上的散热，此催化剂可在更苛可的条件下使用，并且不会引起催化剂过热。因为它扩展了催化剂使用情况的范围，因此它是有益的。As mentioned above, if the catalyst-coated and catalyst-free channels are designed such that the heat transfer surface area between the catalyst-coated channel and the catalyst-free channel divided by the volume of all channels in the catalyst structure is greater than 0.5 mm^-1 , the performance of the catalyst structure of the present invention can be further optimized. Preferably, in the structure of the present invention, the ratio R of the heat transfer area divided by the total channel volume of the catalyst structure between the catalytic channel and the non-catalytic channel is between 0.5mm^-1 to 2mm^-1 , preferably , the R value is between 0.5mm^-1 and 1.5mm^-1 . With a high ratio R of heat transfer surface to total volume, heat transfer is optimized from the catalytic side to the non-catalytic side of the channel walls and into the flowing reaction mixture. The catalyst can be used under more severe conditions without causing the catalyst to overheat due to the optimization of heat dissipation on the catalyst surface by means of integral heat transfer. It is beneficial because it expands the range of catalyst use cases.

本发明催化剂结构件可被设计成在催化和非催化通道间有宽反应混合物物流分布的情况下使用。通过控制催化剂结构件中催化通道与非催化通道的大小和数量，依据催化反应的放热特征和目的转化率范围，10％到90％的总物流可被导入催化通道。较好地，在高放热过程中，像燃料燃烧或部分燃烧，流过催化剂结构件反应混合物物流的比值被控制在35％到70％的物流量通过催化通道，更好地控制50％的物流量通过催化剂结构件的催化通道。在本发明催化剂结构件仅用催化通道的平均D_h小于非催化通道来表征，反应混合物物流分布被控制在催化通道的前开口面积为总前开口面积的20％到80％，同时催化和非催化通道的结构满足催化通道与非催化通道平均D_h的比值小于催化通道与非催化通道前开口面积的比值。如上所述，前开口面积指某给定类型(即催化或非催化)通道在所述催化剂结构件中的平均截面积。该截面积是对通道中反应混合物流开放的，在反应混合物流垂直方向测量的截面积。The catalyst structures of the present invention can be designed to be used with a broad flow distribution of the reaction mixture between the catalytic and non-catalytic channels. By controlling the size and number of catalytic and non-catalytic channels in the catalyst structure, 10% to 90% of the total stream can be directed to the catalytic channels, depending on the exothermic characteristics of the catalytic reaction and the target conversion range. Preferably, in highly exothermic processes, like fuel combustion or partial combustion, the ratio of the reactant mixture flow through the catalyst structure is controlled so that 35% to 70% of the flow passes through the catalytic channels, more preferably 50% of the The stream flows through the catalytic channels of the catalyst structure. The catalyst structure of the present invention is characterized only by the average D_h of the catalyzed passage being less than that of the non-catalyzed passage, and the flow distribution of the reaction mixture is controlled so that the front opening area of the catalyzed passage is 20% to 80% of the total front opening area. Simultaneously, the catalytic and non-catalytic The structure of the catalytic channel satisfies that the ratio of the average D_h of the catalytic channel to the non-catalytic channel is smaller than the ratio of the front opening area of the catalytic channel to the non-catalytic channel. As noted above, front opening area refers to the average cross-sectional area of a given type of passage (ie, catalytic or non-catalytic) in the catalyst structure. The cross-sectional area is the cross-sectional area open to the flow of the reaction mixture in the channel, measured in the direction perpendicular to the flow of the reaction mixture.

对仅由催化通道的h大于非催化通道表征的本发明催化剂结构件。当催化通道在该结构件中占有20％到80％的总前开口面积时，h(cat)/h(non-cat)的比值应大于1.5。优选的此类型结构件的h(cat)/h(non-cat)的比值在1.5到7之间。For catalyst structures of the invention characterized only by h being greater for catalytic channels than for non-catalytic channels. When the catalytic channels occupy 20% to 80% of the total front opening area in the structure, the ratio h(cat)/h(non-cat) should be greater than 1.5. The preferred ratio of h(cat)/h(non-cat) for this type of structure is between 1.5 and 7.

在一个优选的方面，本发明涉及专用于燃料的催化燃烧或部分燃烧的催化剂结构件。这些催化剂结构件的典型特性是整体性且包括许多由耐热支撑材料构成的共用壁，这些共用壁形成了一系列相邻布置的纵向通道以供可燃混合物，如：与含氧气体(像空气)混合形成的气体或蒸汽燃料流通。相邻布置的通道被设计成至少部分通道的至少部分内表面涂有适合氧化可燃混合物的催化剂，即涂催化剂通道，而其余通道未涂催化剂，即无催化剂通道，这样涂催化剂通道的内表面与相邻无催化通道的内表面是换热关系。在本发明这个优选的方面，上述的催化剂结构件的特征在于：涂催化剂通道或催化通道与无催化剂通道或非催化通道在结构上有一个或多个如上描述的关键方面互不相同，因此目的燃烧或氧化反应在催化通道内被促进而在非催化通道内基本上被抑制。其它控制反应的因素与强化传热联合将使催化燃烧过程适用于更宽的操作参数范围，如线速度，入口气体温度和压力。In a preferred aspect, the present invention relates to catalyst structures dedicated to the catalytic combustion or partial combustion of fuels. These catalyst structures are typically monolithic and include a number of common walls of refractory support material forming a series of adjacently arranged longitudinal channels for combustible mixtures such as: ) mixed gas or steam fuel flow. Adjacently arranged channels are designed such that at least part of the inner surface of at least some of the channels is coated with a catalyst suitable for oxidizing a combustible mixture, i.e. a catalyst-coated channel, while the rest of the channels are not coated with a catalyst, i.e. a catalyst-free channel, so that the inner surface of the catalyst-coated channel is in contact with The inner surfaces of adjacent non-catalyzed channels are in heat exchange relationship. In this preferred aspect of the present invention, the above-mentioned catalyst structure is characterized in that: the catalyst-coated channel or catalytic channel and the non-catalyzed channel or non-catalytic channel are structurally different in one or more key aspects as described above, so the purpose Combustion or oxidation reactions are promoted in catalytic channels and substantially inhibited in non-catalytic channels. Other factors controlling the reaction combined with enhanced heat transfer will make the catalytic combustion process applicable to a wider range of operating parameters such as line velocity, inlet gas temperature and pressure.

在本发明这个优选方面，催化剂结构件是一种在陶瓷或金属整材上的铂族金属基催化剂。该整材支撑件的安装使得催化和非催化通道从支撑件一端纵向延伸到另一端，这样可使可燃气从一端通过整个通道长度流到另一端。至少部分内表面涂催化剂的催化通道无需涂布其全长。未涂催化剂的通道或非催化通道的内壁上没有催化剂或仅有无活性或者极低活性的涂层在其壁上。In this preferred aspect of the invention, the catalyst structure is a platinum group metal based catalyst on a ceramic or metal monolith. The monolithic support is mounted such that the catalytic and non-catalytic channels extend longitudinally from one end of the support to the other, which allows the combustible gas to flow from one end to the other through the entire length of the channel. Catalytic channels that are at least partially coated with catalyst on their inner surfaces need not be coated over their entire length. Uncoated channels or non-catalyzed channels have no catalyst or only an inactive or very low activity coating on the walls.

适宜用于催化剂结构件中的支撑件材料可以是常见耐热、惰性材料，如陶瓷，耐热无机氧化物，金属互化物，碳化物，氮化物或金属材料。优选的支撑件是耐高温金属互化物或金属材料。这些材料是有强度且可延展的，易于安装和联接而形成结构件以及由于它们比陶瓷材料更易制成较薄的壁而使单位截面积可提供更大的流动空间。优选的金属互化材料包括金属铝化物，如镍铝化物和钛铝化物，而适宜的金属支撑件材料包括铝，耐高温合金、不锈钢，含铝钢和含铝合金。耐高温合金可以是镍或钻合金或其它可用于高温的合金。若使用耐热无机氧化物作为支撑件材料，适宜的选择可以是氧化硅、氧化铝、氧化镁、氧化锆和这些材料的混合物。The support material suitable for use in the catalyst structure can be common heat-resistant and inert materials, such as ceramics, heat-resistant inorganic oxides, intermetallic compounds, carbides, nitrides or metal materials. A preferred support is a refractory intermetallic or metallic material. These materials are strong and malleable, easy to install and join to form structural members and provide more room for flow per unit cross-sectional area because they are easier to make with thinner walls than ceramic materials. Preferred intermetallic materials include metal aluminides, such as nickel aluminides and titanium aluminides, while suitable metal support materials include aluminum, high temperature resistant alloys, stainless steel, aluminized steel and aluminum alloys. The high temperature resistant alloy can be nickel or cobalt alloy or other alloys that can be used for high temperature. If a refractory inorganic oxide is used as the support material, suitable choices may be silica, alumina, magnesia, zirconia and mixtures of these materials.

优选的材料是含铝钢，例如：下面专利中公开的材料，Aggen等人的美国专利4,414,023，Chapman等人的美国专利4,331,631，和Cairns等人的美国专利3,969,082。这些钢和出售的其他钢Kawasaki steel Corporation(River Lite 2-5-SR)，VereinigteDeutchse Metallwerke AG(Alumchrom I RE)和Allegheny LudiumSteel(Alfa-V)含有足够的溶解铝以致于当氧化时，铝形成了氧化铝晶须，晶体或钢表面上的膜层，它们提供了一种粗糙的和有化学反应活性的表面以更好地粘连催化剂或催化剂基层。Preferred materials are aluminum-containing steels such as those disclosed in US Patent 4,414,023 to Aggen et al, US Patent 4,331,631 to Chapman et al, and US Patent 3,969,082 to Cairns et al. These steels and others sold by Kawasaki Steel Corporation (River Lite 2-5-SR), Vereinigte Deutchse Metallwerke AG (Alumchrom I RE) and Allegheny LudiumSteel (Alfa-V) contain enough dissolved aluminum that when oxidized, the aluminum forms Alumina whiskers, crystals or films on steel surfaces that provide a rough and chemically reactive surface for better adhesion to catalyst or catalyst substrates.

对于本发明优选方面的催化剂结构件，可用通常的技术加工金属或金属互化物支撑件材料，以形成蜂窝结构、波纹板的螺旋卷或叠置型结构，用平板或其它结构的板形成内层压结构、柱状结构和其它形式的结构，这些结构产生了相邻纵向通道，这些通道是按照前述设计标准设计成的流动通道。若使用金属互化物或金属薄板或波纹板，则仅在薄板或板的一边涂催化剂，或者在某些情况下依据设计催化剂结构的要求不在板或薄板上涂催化剂。仅对板或薄板的一边涂催化剂然后制造催化剂结构件是利用了整体换热的概念，这将使催化剂上产生的热流过结构件壁并与在相对一边非催化壁上流动的气体接触，从而促进热量移出催化剂并保持催化剂温度低于完全绝热反应温度，在此，绝热燃烧温度是指完全反应且气体混合物无热量损失时气体混合物的温度。For the catalyst structures of the preferred aspects of the invention, the metal or intermetallic support material can be processed by conventional techniques to form honeycomb structures, spiral wound or stacked structures of corrugated sheets, and inner laminates with flat or other structured sheets Structures, columnar structures, and other forms of structures that create adjacent longitudinal channels that are flow channels designed in accordance with the aforementioned design criteria. If intermetallic or metal sheets or corrugated sheets are used, only one side of the sheet or sheet is coated with catalyst, or in some cases no catalyst is applied to the sheet or sheet as required by the design catalyst structure. Catalyzing only one side of a plate or sheet and then making a catalyst structure utilizes the concept of integral heat transfer, which allows the heat generated on the catalyst to flow through the wall of the structure and come into contact with the gas flowing on the opposite non-catalytic wall, thereby Facilitates the removal of heat from the catalyst and maintains the catalyst temperature below the fully adiabatic reaction temperature, where the adiabatic combustion temperature is the temperature of the gas mixture when the reaction is complete and there is no heat loss from the gas mixture.

在许多情况下，对用于燃烧过程的催化剂结构件，在沉积催化剂之前，在支撑件壁上涂一个基层是有用的，并能改善催化剂的稳定性和性能。涂布这种基层可使用本领域描述的方法，例如，涂布γ-氧化铝、氧化锆、氧化硅、氧化钛材料(较好为溶胶)或含下列物质的至少二种氧化物的混合溶胶：铝、硅、钛、锆和添加剂如钡、铈、镧、铬或各种其他组分。为更好地粘附基层，可在支撑件壁上涂含有水合氧化物如Chapman等人在美国专利4,279,782中描述的假一水软铝氧化铝稀释悬浮液的底涂层。涂底涂层的表面可先涂布γ-氧化铝悬浮液，再干燥，然后熔烧以在金属表面产生高表面积附着氧化膜。然而，最好使用氧化锆溶胶或悬浮液做为基层。其它耐火氧化物，如氧化硅和氧化钛也是适用的。对一些铂族金属如铂，最优选的是氧化锆/氧化硅混合溶胶，其中两者在涂到支撑件上前混合。In many cases, for catalyst structures used in combustion processes, it is useful to coat the walls of the support with a base layer prior to catalyst deposition and to improve catalyst stability and performance. This base layer can be coated with methods described in the art, for example, coating gamma-alumina, zirconia, silicon oxide, titanium oxide material (preferably sol) or a mixed sol containing at least two oxides of the following substances : Aluminum, silicon, titanium, zirconium and additives such as barium, cerium, lanthanum, chromium or various other components. For better adhesion to the base layer, the support walls may be coated with a primer containing a dilute suspension of a hydrous oxide such as the pseudomonohydric alumina described by Chapman et al. in US Pat. No. 4,279,782. The surface to be primed can be coated with a gamma-alumina suspension, dried, and then sintered to produce a high surface area adherent oxide film on the metal surface. However, it is preferred to use a zirconia sol or suspension as the base layer. Other refractory oxides such as silicon oxide and titanium oxide are also suitable. For some platinum group metals such as platinum, the most preferred is a zirconia/silica hybrid sol where the two are mixed prior to coating onto the support.

可用与涂漆到表面上相同的方式涂布基层，例如，喷涂，直接涂或将支撑件浸入基层物质中等方法。The substrate can be applied in the same manner as painting onto a surface, for example, by spraying, direct coating or dipping the support into the substrate substance.

铝结构件也适宜用于本发明，并且基本上可用同样的方式进行处理或涂布。铝合金有些过于可塑，并且在本方法的应用温度范围内可能变型或甚至熔化。因此，它很少用作支撑件，但若温度条件适宜便可使用。Aluminum structural parts are also suitable for use in the present invention and can be treated or coated in essentially the same manner. Aluminum alloys are somewhat too malleable and may deform or even melt within the application temperature range of the method. Therefore, it is rarely used as a support, but it can be used if the temperature conditions are favorable.

对含铝铁类金属，金属板可在空气中进行热处理，从而导致其表面生长晶须。此种晶须可增大后续膜的附着力或增加了催化剂直接涂布的表面积。随后，在此金属板上喷涂氧化铝、氧化硅、氧化锆、氧化钛和一种耐热金属氧化物悬浮液或一种或几种氧化硅、氧化锆、氧化钛或耐热金属氧化物材料而形成的混合物，并经干燥和熔烧形成了一种具有高表面积的基层。然后，按同样方式在基层上涂催化剂，即通过向金属板的基层上喷涂、浸涂或涂抹催化组分的溶液、悬浮液或混合物。For aluminum-containing ferrous metals, the metal plate can be heat-treated in air, causing whiskers to grow on its surface. Such whiskers may increase the adhesion of subsequent films or increase the surface area for direct coating of the catalyst. Subsequently, this metal plate is sprayed with aluminum oxide, silicon oxide, zirconium oxide, titanium oxide and a refractory metal oxide suspension or one or more silicon oxide, zirconium oxide, titanium oxide or refractory metal oxide materials The resulting mixture is dried and fired to form a substrate with a high surface area. The catalyst is then applied to the substrate in the same manner, ie by spraying, dipping or spreading a solution, suspension or mixture of catalytic components onto the substrate of the metal plate.

催化剂物质也可以混合在基层物质中并涂布在支撑件上，从而部分地省略了另外加入催化剂的步骤。The catalyst material can also be mixed in the base layer material and coated on the support, thereby partially omitting the additional step of adding catalyst.

在催化燃烧应用中，当相当大部分燃烧是在气体离开催化剂后进行时，催化剂结构件可制做成满足离开催化剂的气体温度不高于1000℃，优选在700℃到950℃之间。该优选的温度取决于燃料、压力和特定的燃烧器设计。催化剂可在催化材料上含有一种非催化扩散阻挡层，如美国专利5,232,357中所述。In catalytic combustion applications, where a substantial portion of the combustion takes place after the gas leaves the catalyst, the catalyst structure can be fabricated such that the temperature of the gas leaving the catalyst is not higher than 1000°C, preferably between 700°C and 950°C. The preferred temperature depends on the fuel, pressure and specific burner design. The catalyst may contain a non-catalytic diffusion barrier on the catalytic material, as described in US Pat. No. 5,232,357.

复合物即催化剂结构件中催化金属含量一般很少，例如，0.01％到15％(重量)，优选0.01％到10％(重量)。虽然许多氧化催化剂在这种应用中是适宜的，但VIII族贵金属或铂族金属(钯、钌、铑、铂、锇和铱)是优选的。更好地是钯(由于其自我限制燃烧温度的能力)和铂。这些金属可单独或混合使用。钯和铂的混合物是符合需要的，这是因为它们生成的催化剂具有钯的限制温度能力，虽然限制温度值不同；并且该混合物很少因与燃料中杂质反应或者与催化剂支撑件反应而失活。The catalytic metal content of the composite, ie catalyst structure, is generally low, for example, 0.01% to 15% by weight, preferably 0.01% to 10% by weight. While many oxidation catalysts are suitable for this application, Group VIII noble metals or platinum group metals (palladium, ruthenium, rhodium, platinum, osmium and iridium) are preferred. More preferred are palladium (due to its ability to self-limit the combustion temperature) and platinum. These metals can be used alone or in combination. Mixtures of palladium and platinum are desirable because they produce catalysts that have the temperature-limiting capabilities of palladium, albeit at different values; and the mixture is less deactivated by reaction with impurities in the fuel or with the catalyst support .

可通过各种不同的方法使用贵金属配合物、化合物或金属分散体在本发明催化剂结构件的支撑件上加入铂族金属或元素。这些化合物或配合物是烃类可溶解的水溶液。金属可从溶液中析出。一般地，利用蒸发或分解可将载液从催化剂载体中除去，同时将金属以分散的形式留在支撑件上。The incorporation of platinum group metals or elements on the support of the catalyst structure of the invention can be done by various methods using noble metal complexes, compounds or metal dispersions. These compounds or complexes are aqueous solutions in which hydrocarbons are soluble. Metals can come out of solution. Generally, the carrier liquid is removed from the catalyst support by evaporation or decomposition, while leaving the metal in dispersed form on the support.

适宜的铂族金属化合物是氯铂酸、钾铂氯化物、硫氰酸铂铵、氢氧化四铵铂，铂族金属氯化物、氧化物、硫化物、硝酸盐、氯化四铵铂、亚硝酸铂铵、氯化四铵钯，氯化铑和氯化六胺铱。当制备本发明催化剂时，若需用金属混合物，它们可以是水溶解形式，例如像氢氧化胺或像氯铂酸和硝酸钯的形式。在催化剂组合物中，铂族金属可以元素或化合形式如氧化物或硫化物存在。在后续处理中，如焙烧或使用时，基本上全部铂族金属都转化成元素形式。Suitable platinum group metal compounds are chloroplatinic acid, potassium platinum chloride, platinum ammonium thiocyanate, tetraammonium platinum hydroxide, platinum group metal chlorides, oxides, sulfides, nitrates, tetraammonium platinum chloride, Platinum Ammonium Nitrate, Tetraammonium Palladium Chloride, Rhodium Chloride, and Hexamine Iridium Chloride. When preparing the catalysts of the invention, metal mixtures, if desired, may be in water-soluble form, for example as ammonium hydroxide or as chloroplatinic acid and palladium nitrate. In the catalyst composition, the platinum group metals may be present in elemental or compound form such as oxides or sulfides. During subsequent processing, such as firing or use, substantially all of the platinum group metals are converted to elemental form.

此外，在催化剂结构件中首先接触可燃气体的部分放置更高活性的催化剂，较好地是钯，催化剂将更被“激活”(light off)且在结构件的后来区域不产生“热点”(hot spots)。由于在引导位置施用较多的催化剂和具有较大的表面积或其它措施，引导位置的活性较高。Furthermore, by placing a more active catalyst, preferably palladium, in the part of the catalyst structure that first contacts the combustible gas, the catalyst will be more "lighted off" and will not create "hot spots" in later areas of the structure ( hot spots). The activity of the piloted site is higher due to the application of more catalyst at the piloted site and having a larger surface area or other measures.

在催化燃烧应用中，本发明催化剂结构件的尺寸和结构应满足：气体通过催化剂结构件中纵向通道的平均线速度在整个催化结构中大于0.2m/second，但不超过80m/second。此下限大于甲烷在350℃空气中火焰前部速度而上限是目前可获得的商业支撑件的实际值。这些平均速度对不是甲烷的燃料而言稍有不同。低速燃烧的燃料允许使用较小的最小和最大线速度。In the catalytic combustion application, the size and structure of the catalyst structure of the present invention should satisfy: the average linear velocity of gas passing through the longitudinal channel in the catalyst structure is greater than 0.2m/second in the entire catalytic structure, but not more than 80m/second. This lower limit is greater than the flame front velocity of methane in air at 350°C and the upper limit is the actual value of currently available commercial supports. These average velocities are slightly different for fuels other than methane. Slow burning fuels allow the use of smaller minimum and maximum linear velocities.

依据反应混合物的特性，在催化剂结构件中使用的通道平均尺寸变化很大。对催化燃烧，适宜的催化剂结构件每平方英寸含有50到600个通道。较好地，催化剂结构件每平方英寸含有150到450个通道。Depending on the properties of the reaction mixture, the average size of the channels used in the catalyst structure can vary widely. For catalytic combustion, suitable catalyst structures contain 50 to 600 channels per square inch. Preferably, the catalyst structure contains 150 to 450 channels per square inch.

使用本发明催化剂结构件的本发明催化燃烧方法可适用于各种燃料且可在很宽的工艺条件下操作。The catalytic combustion method of the present invention using the catalyst structure of the present invention is applicable to various fuels and can be operated under a wide range of process conditions.

虽然通常的气体烃类，即甲烷、乙烷和丙烷是本方法的最好燃料源，大多数在如下讨论的工艺温度下能气化的燃料都是可适用的，例如，在室温和常压下是气体或液体的燃料。实例包括了上述低分子量烃类和丁烷、戊烷、己烷、庚烷、辛烷、汽油，芳香烃类，如苯、甲苯、乙基苯、二甲苯、石脑油、柴油机燃料、煤油、喷气燃料，其它中等馏分、重质馏分燃料(较好为氢化处理除去含氮和含硫化合物)，含氧燃料，如醇类，包括甲醇、乙醇、异丁醇、丁醇或其它醇，醚类，如二乙基醚，乙基苯基醚，MTBE等。低BTU气，如家用煤气或合成气，也可用做燃料。Although the usual gaseous hydrocarbons, i.e., methane, ethane and propane, are the best fuel sources for this process, most fuels that vaporize at the process temperatures discussed below are applicable, e.g., at room temperature and pressure Below are gas or liquid fuels. Examples include the low molecular weight hydrocarbons mentioned above and butane, pentane, hexane, heptane, octane, gasoline, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, naphtha, diesel fuel, kerosene , jet fuel, other middle-distillate and heavy-distillate fuels (preferably hydrotreated to remove nitrogen and sulfur-containing compounds), oxygenated fuels, such as alcohols, including methanol, ethanol, isobutanol, butanol or other alcohols, Ethers, such as diethyl ether, ethyl phenyl ether, MTBE, etc. Low BTU gases, such as household gas or syngas, can also be used as fuel.

通常，燃料以一定量混合在燃烧空气中，该量应能产生的混合物具有理论绝热燃烧温度Tad大于用于本发明方法中催化剂的温度或催化剂中气相温度。优选此绝热燃烧温度高于900℃，最优选高于1000℃。非气体燃料应在它们接触初始催化剂区以前被汽化。燃烧空气可被压缩到500psig或更高的压力。固定气体透平常运转在150psig压力附近。Typically, the fuel is mixed with the combustion air in an amount that produces a mixture having a theoretical adiabatic combustion temperature Tad greater than the temperature of the catalyst used in the process of the invention or the temperature of the gas phase in the catalyst. Preferably the adiabatic combustion temperature is above 900°C, most preferably above 1000°C. Non-gaseous fuels should be vaporized before they contact the initial catalyst zone. Combustion air can be compressed to 500 psig or higher. Fixed gas turbines normally operate at around 150 psig.

本发明方法可在使用本发明催化剂结构件的单个催化反应区域或使用专为每个催化阶段设计的催化剂结构件的多个催化反应区，通常是2或3进行。在大多数情况下，催化反应区后跟着一个均相燃烧区，在这里离开前面催化燃烧区的气体在非催化、无火焰的条件下燃烧以提供气体透平所需要的较高的气体温度，例如1000到1500℃范围内的温度。The process of the present invention can be carried out in a single catalytic reaction zone using the catalyst structure of the present invention or in multiple catalytic reaction zones, usually 2 or 3, using catalyst structures specially designed for each catalytic stage. In most cases, the catalytic reaction zone is followed by a homogeneous combustion zone, where the gas leaving the previous catalytic combustion zone is burned under non-catalytic, flameless conditions to provide the higher gas temperature required by the gas turbine, For example temperatures in the range 1000 to 1500°C.

均相燃烧区的尺寸应设计成实现完全燃烧并将一氧化碳减少到期望的浓度。催化剂后反应区的气体停留时间是2到100ms，较好地是10到50ms。The homogeneous combustion zone should be sized to achieve complete combustion and reduce carbon monoxide to the desired concentration. The gas residence time in the reaction zone after the catalyst is 2 to 100 ms, preferably 10 to 50 ms.

现在参见附图，图1和2描述了二个常规的使用整体换热催化剂结构件的重复单元端视图。所示的重复单元在完整的催化剂结构件中将以叠置或层压状形式出现。图1中，支撑件由二个金属板或带组成。一个(10)具有起伏的或波纹的结构形式，另一个(12)是平板。波纹形成的波峰和波谷沿纵向扩展跨过板的宽度，并且上下两侧的波纹板堆靠在平板上以形成直线纵向通道(14和16)，该通道扩展跨过叠置或堆靠板的宽度。此处所示的起伏或正弦波纹形式仅为示意。此波纹可是正弦的、三角的或其它常规形式。起伏板(10)底部和平板(12)顶部涂催化剂或基层加催化剂(18)，从而当各板按所示叠置在一起时，涂催化剂通道(14)和无催化剂通道(16)是整体换热关系。如上指出，所形成的催化通道(14)和非催化通道(16)基本上是直线和不变横截面积的。此结构件提供的催化和非催化通道中，催化通道与非催化通道的平均D_h的比值为1，并且h(cat)/h(non-cat)比值也是1。Referring now to the drawings, Figures 1 and 2 depict end views of two conventional repeating units utilizing integral heat exchange catalyst structures. The repeat units shown will occur in stacked or laminated form in the complete catalyst structure. In Figure 1, the support consists of two metal plates or strips. One (10) has an undulating or corrugated structure and the other (12) is a flat plate. The crests and troughs of the corrugations extend longitudinally across the width of the plates, and the upper and lower corrugated plates are stacked against the plates to form straight longitudinal channels (14 and 16) that extend across the width of the stacked or stacked plates. width. The undulating or sinusoidal corrugation patterns shown here are for illustration only. This corrugation may be sinusoidal, triangular or other conventional form. The bottom of the undulating plate (10) and the top of the flat plate (12) are catalyst-coated or base-plus-catalyst (18) so that when the plates are stacked together as shown, the catalyst-coated channels (14) and the catalyst-free channels (16) are integral heat transfer relationship. As noted above, the formed catalytic channels (14) and non-catalytic channels (16) are substantially rectilinear and of constant cross-sectional area. Among the catalytic and non-catalytic channels provided by this structure, the ratio of the average D_h of the catalytic channel to the non-catalytic channel is 1, and the ratio of h(cat)/h(non-cat) is also 1.

图2所示重复单元包括二个具有人字型波纹、沿纵向扩展跨过板长的波纹金属板(20和22)。一个波纹板(22)在其顶部一测涂有催化剂，另一个波纹板底部一测涂有催化剂，以致于当这些板以非嵌套叠置在一起时，涂催化剂通道(26)与无催化剂通道(28)形成了整体换热。The repeating unit shown in Figure 2 comprises two corrugated metal sheets (20 and 22) having herringbone corrugations extending longitudinally across the length of the sheet. One corrugated plate (22) is coated with catalyst on its top side and the bottom side of the other corrugated plate is coated with catalyst, so that when these plates are stacked together in a non-nested manner, the catalyst-coated channel (26) is separated from the catalyst-free channel (26). The channels (28) form an integral heat exchange.

图3进一步显示了人字型波纹形式金属板的细节。这种板适宜用在以上图2所示的结构件中或者当人字波纹是用于将曲折度引入催化通道时，它也可适用于本发明结构件中。从图3示意的侧视图、顶视图和俯视图中可见，该板是起伏的以产生波峰(30)和波谷(32)，它们沿板宽度形成了人字形式。图2和3所示三角波纹形式仅为示意。此波纹可是三角形的，正弦形的或其它本领域可预见的波纹形式。Figure 3 shows further details of the metal plate in the form of herringbone corrugations. Such a plate is suitable for use in the structure shown in Figure 2 above or it may also be suitable for use in the structure of the present invention when the chevrons are used to introduce tortuosity into the catalytic channels. As can be seen in the schematic side, top and plan views of Figure 3, the panel is undulating to produce peaks (30) and troughs (32) which form a herringbone pattern along the width of the panel. The triangular corrugation forms shown in Figures 2 and 3 are for illustration only. The corrugations may be triangular, sinusoidal or other corrugation forms foreseeable in the art.

图2所示的波纹板的非嵌套性质和人字型波纹的效果以及催化和非催化通道沿其长度上各点的形状在图3A、3B和3C中进一步说明。这些图显示了重复单元端视图(图3A，它与图2一样)的截面图，也显示了通道纵轴增量点的截面图(图3B和3C)，在这里叠置人字型波纹的方向取向差异引起每块板上波纹形成的波峰和波谷的位置相对于该重复单元中直接在该板上下两侧的波纹的波峰和波谷的位置发生变化。在图3A中，催化通道(26)和非催化通道(28)具有重复的V形截面积，图3B中，由相邻人字型波纹的波峰和波谷的取向不同而引起的通道壁取向的变化导致通道(26和28)是方形横截面。最后，在图3C中，在某给定板人字波纹形成的波峰和波谷分别直接与相邻上下板的波谷和波峰接触，这就是说，相邻板上的人字波纹跨在另一板上，催化通道(26)和非催化通道(28)具有钻石形的横截面。当然，这种通道截面形状变化的模式将反复重复直到非嵌套人字波纹限定的通道全长度。在这种情况下，即使非嵌套人字波纹导致通道沿其长度有一个变化的截面积，催化和非催化通道沿其长度显示了相同的变化。因此，图2所示结构件提供的催化和非催化通道中，催化通道的平均D_h等于非催化通道的平均D_h，并且h(cat)/h(non-cat)比值是1。The non-nested nature of the corrugated sheets shown in Figure 2 and the effect of the herringbone corrugations and the shape of the catalytic and non-catalytic channels at various points along their length are further illustrated in Figures 3A, 3B and 3C. These figures show cross-sections of the repeating unit end view (Fig. 3A, which is the same as Fig. 2), and also cross-sections at incremental points along the longitudinal axis of the channel (Figs. 3B and 3C), where the herringbone corrugations are superimposed. The directional orientation difference causes the position of the crests and troughs formed by the corrugations on each plate to vary relative to the crests and troughs of the corrugations in the repeating unit directly above and below the plate. In Fig. 3 A, catalytic channel (26) and non-catalytic channel (28) have repeated V-shaped cross-sectional area, and among Fig. 3 B, the orientation difference of channel wall caused by the different orientations of crests and troughs of adjacent herringbone corrugations The variation results in channels (26 and 28) being square in cross-section. Finally, in Figure 3C, the crests and troughs formed by the herringbone corrugations on a given plate are directly in contact with the troughs and crests of the adjacent upper and lower plates respectively, that is to say, the herringbone corrugations on the adjacent plate straddle the other plate Above, the catalytic channels (26) and the non-catalytic channels (28) have diamond-shaped cross-sections. Of course, this pattern of channel cross-sectional shape changes will repeat over and over until the full length of the channel is defined by the non-nested chevrons. In this case, even though the non-nested chevrons cause the channel to have a varying cross-sectional area along its length, the catalytic and non-catalytic channels show the same variation along their length. Thus, of the catalytic and non-catalytic channels provided by the structure shown in Figure 2, the average D_h of the catalytic channels is equal to the average D_h of the non-catalytic channels, and the ratio h(cat)/h(non-cat) is unity.

图4显示了本发明催化剂结构件重复单元的端视图，其中一系列各种结构的金属板叠置在一起并使催化通道在结构上与非催化通道不同。重复单元包括二个平板(40)的组合，一个形成直线通道的直线波纹板(42)和二个有人字波纹的波纹板(44)。利用选择性地在二平板的一侧和波纹板之一的一侧涂催化剂，从而形成了催化通道(46)和非催化通道(48)。从图中可见，非催化通道是通过将二个直线通道板平板叠置形成以提供开放通道。相反，催化通道是在两个平板间非嵌套叠置人字波纹薄板或板形成的，从而使通道具有曲折的流动路径并有一个较小的D_h 。具有下列实施例2给出尺寸的本结构件提供了催化通道与非催化通道的平均D_h之比值是0.66，且h(cat)/h(non-cat)比值是2.53的催化和非催化通道。在这种情况下，催化通道与非催化通道间的传热面积除以结构件中总体积的比值0.30mm^-1。Figure 4 shows an end view of a repeating unit of a catalyst structure of the present invention wherein a series of metal plates of various configurations are stacked together and the catalytic channels are structurally distinct from the non-catalytic channels. The repeating unit comprises a combination of two flat plates (40), a linear corrugated plate (42) forming a straight channel and two corrugated plates (44) with herringbone corrugations. Catalytic channels (46) and non-catalytic channels (48) are formed by selectively coating one side of two flat plates and one side of corrugated plates with catalyst. As can be seen from the figure, the non-catalytic channels are formed by stacking two rectilinear channel plate plates to provide open channels. In contrast, catalytic channels are formed by non-nested stacking of herringbone corrugated sheets or plates between two flat plates so that the channels have a tortuous flow path and a small_Dh . The present structure with the dimensions given in Example 2 below provided catalytic and non-catalytic channels with an average_D ratio of 0.66 and a h(cat)/h(non-cat) ratio of 2.53. . In this case, the ratio of the heat transfer area between the catalytic channel and the non-catalytic channel divided by the total volume in the structure is 0.30 mm^-1 .

图5描绘了本发明优选的催化剂结构件重复单元的端视图，重复单元叠置形成催化剂结构件。该重复单元由三种不同类型的波纹金属板组成(52，54a和54b)。第一种类型的波纹板(52)基本上是一个平板，平板延伸的平坦区域周期性地被尖波峰的波纹隔断，并且该波纹直线跨过平板形成了直线波纹。第二种类型的波纹板(54a和54b)由一系列人字型波纹组成。在所示重复单元中，两个人字波纹板以非嵌套形式叠置在具有宽的平板区域的被尖波峰波纹分开的平板顶部。此外，第二块有尖峰波纹的平板叠置在以非嵌套波纹人字型叠置的在一起的上部的波纹板的顶部。催化剂(56)涂在每个有尖波峰波纹板底部和下面人字形波纹板的顶部，从而形成了具有小水力学直径和曲折流动通道的催化通道(58a和58b)和基本上是直线波纹的、更大、更开放的非催化通道(60)。若该催化剂结构件制做成实施例3中给定尺寸的结构件，则催化通道与非催化通道的平均D_h的比值是0.41，同时h(cat)/h(non-cat)比值是1.36。进一步说，催化和非催化通道间传热面积除以实施例3给定尺寸结构件中的总通道体积的比值是0.74。Figure 5 depicts an end view of a preferred catalyst structure repeat unit of the present invention stacked to form the catalyst structure. The repeating unit consists of three different types of corrugated metal sheets (52, 54a and 54b). A first type of corrugated plate (52) is essentially a flat plate with extended flat areas periodically interrupted by corrugations with sharp peaks and the corrugations forming straight corrugations straight across the plate. The second type of corrugated sheet (54a and 54b) consists of a series of herringbone corrugations. In the repeating unit shown, two herringbone corrugated panels are stacked in a non-nesting fashion on top of panels having wide panel areas separated by sharp crest corrugations. Additionally, a second sheet of peaked corrugation is stacked on top of the upper corrugated sheet stacked together in a non-nesting corrugation herringbone pattern. Catalyst (56) is coated on the bottom of each peaked corrugated sheet and the top of the lower herringbone corrugated sheet, thereby forming catalytic channels (58a and 58b) with small hydraulic diameters and tortuous flow paths and substantially straight corrugated , larger, more open non-catalytic channels (60). If the catalyst structure is made into a structure of the given size in Example 3, the ratio of the average D_h of the catalyzed passage to the non-catalyzed passage is 0.41, while the h(cat)/h(non-cat) ratio is 1.36 . Further, the ratio of the heat transfer area between the catalytic and non-catalytic channels divided by the total channel volume in a structure of a given size in Example 3 was 0.74.

图5所示的优选的催化剂结构件很容易通过在二个具有尖波峰波纹平板间插入其它人字形波纹的波纹板改型以增加催化通道的数量和曲折度。若在此重复单元中插入另外的波纹板(将图中所示两块板以非嵌套形式叠置)，依据催化剂结构件的要求可涂其中一块板的一边或不涂。The preferred catalyst structure shown in Figure 5 is easily modified by inserting additional herringbone corrugations between two corrugated plates with sharp crests to increase the number and tortuosity of the catalytic channels. If additional corrugated sheets are inserted in this repeating unit (the two sheets shown in the figure are stacked in a non-nested form), one side of one of the sheets can be coated or not, depending on the requirements of the catalyst structure.

图6显示了另一种本发明结构件重复单元的进口端视图。如图所示，支撑件由二个基本平的金属板(62)其中水平平坦区域被竖板周期性地隔开以形成大的、开放的区域和在二个基本平的板之间以非嵌套形式叠置的三个人字波纹金属波纹板(64，66，68)制成。这三个波纹板波纹程度不同，也就是单位宽度的波纹数目不同，在顶部和中部的波纹板(64和66)波纹程度大于底部的波纹板(68)。催化剂(70)涂在二个基本为平板(62)底部，顶部波纹板(64)的底部，底部波纹板(68)的顶部。从而产生了基本为直线结构的、大的、开放的非催化通道(72)和具有很小平均D_h及曲折流动路径结构的三个催化通道(74，76和78)。此结构件中，板(62)的高是1.6mm，平坦区域为3.3mm；板(68)的高是0.41mm，波峰到波峰的间隔是0.66mm；板(66)的高是0.69mm，波峰到波峰的间隔是0.31mm；催化通道与非催化通道的平均D_h的比值是1.5而且h(cat)/h(non-cat)比值是2.72。在这情况下，催化通道和非催化通道间的换热面积除以结构件中全部通道体积的比值是0.91mm^-1。Figure 6 shows an inlet end view of another structural member repeating unit of the present invention. As shown, the support consists of two substantially flat metal plates (62) with horizontal planar areas periodically separated by risers to form large, open areas and between the two substantially flat It is made of three herringbone corrugated metal corrugated plates (64, 66, 68) stacked in a nested form. These three corrugated plates have different corrugation degrees, that is, the number of corrugations per unit width is different, and the corrugated plates (64 and 66) at the top and middle are more corrugated than the corrugated plates (68) at the bottom. The catalyst (70) is coated on the bottom of two substantially flat plates (62), the bottom of the top corrugated plate (64), and the top of the bottom corrugated plate (68). This results in a large, open non-catalytic channel (72) of substantially rectilinear configuration and three catalytic channels (74, 76 and 78) with a small average_Dh and tortuous flow path configuration. In this structural member, the height of the plate (62) is 1.6mm, and the flat area is 3.3mm; the height of the plate (68) is 0.41mm, and the interval between peaks and peaks is 0.66mm; the height of the plate (66) is 0.69mm, The peak-to-peak spacing is 0.31 mm; the average D_h ratio of catalyzed to non-catalyzed channels is 1.5 and the h(cat)/h(non-cat) ratio is 2.72. In this case, the ratio of the heat transfer area between the catalytic channels and the non-catalytic channels divided by the volume of all the channels in the structure is 0.91 mm⁻¹ .

依据前述设计规范，本领域技术人员可制做本发明范围内的各种催化剂结构件。其它可能的结构件可见图7，图8，其中示出的重复单元的端视图。图7中，人字形波纹的金属波纹板(80和82)以非嵌套形式叠置在波纹板(84)之间，波纹板(84)具有在整板长度上沿纵向直线方向扩展的波峰和波谷。催化剂(86)涂在顶部波纹板(80)的底部和底部波纹板(82)顶部，从而使小平均D_h和大曲折度的催化通道(88)与较大的、更开放的基本直线流动路径的非催化通道(90)之间形成整体换热关系。According to the aforementioned design specifications, those skilled in the art can manufacture various catalyst structures within the scope of the present invention. Other possible structural members can be seen in Figures 7 and 8, which show an end view of the repeating unit. In Fig. 7, metal corrugated plates (80 and 82) of herringbone corrugation are stacked in a non-nested form between corrugated plates (84), and the corrugated plates (84) have crests extending along the longitudinal linear direction on the entire length of the plate and trough. Catalyst (86) is coated on the bottom of the top corrugated sheet (80) and on top of the bottom corrugated sheet (82) such that the catalytic channels (88) with small average_Dh and large tortuosity are compared with larger, more open substantially straight flow An integral heat transfer relationship is formed between the non-catalytic channels (90) of the pathway.

图8中，三个人字波纹型的金属波纹板(92.94和96)以非嵌套形式叠置在与图7结构件所用波纹板结构相似的直线通道金属波纹板之间。催化剂(100)涂在顶部波纹板(92)的底部和底部波纹板(96)的顶部，从而使具有小平均D_h和曲折度的涂催化剂通道(102)与较大的、开放的基本直线流动路径的无催化剂通道(104)之间形成整体换热关系。In Fig. 8, three herringbone corrugated metal corrugated plates (92.94 and 96) are stacked in a non-nested form between linear channel metal corrugated plates similar in structure to the corrugated plate used in the structural member in Fig. 7 . Catalyst (100) is coated on the bottom of the top corrugated sheet (92) and on top of the bottom corrugated sheet (96), such that the catalyst-coated channels (102) with small average_Dh and tortuosity are compared to larger, open, substantially straight An integral heat exchange relationship is formed between the catalyst-free channels (104) of the flow path.

                      实施例Example

如下实施例通过与常规使用整体换热的催化剂比较证明使用本发明催化剂结构件取得的进步。The following examples demonstrate the progress made using the catalyst structures of the present invention by comparison with conventional catalysts using integral heat exchangers.

                      实施例1Example 1

利用图2所示常规催化剂结构件，按如下方法制备催化剂并在汽油型燃料的燃烧中测试该催化剂。Using the conventional catalyst structure shown in Fig. 2, a catalyst was prepared and tested in the combustion of gasoline-type fuel as follows.

首先将20.8g原硅酸四乙基酯与4.57cc的2mM硝酸以及12.7g乙醇混合后制备SiO₂/ZrO₂粉末。将此混合物加到比表面积为100m²/gm的100g氧化锆粉末中。此制得固体物在密封玻璃容器中陈化一天并干燥。一部分在1000℃空气中焙烧，另一部分在1000℃空气中焙烧。Firstly, SiO₂ /ZrO₂ powder was prepared by mixing 20.8g of tetraethyl orthosilicate, 4.57cc of 2mM nitric acid and 12.7g of ethanol. This mixture was added to 100 g of zirconia powder having a specific surface area of 100 m² /gm. The resulting solid was aged in a sealed glass container for one day and dried. One part was fired in air at 1000°C, and the other part was fired in air at 1000°C.

将152g，1000℃下焙烧的SiO₂/ZrO₂粉末与15.2g，500℃下焙烧的SiO₂/ZrO₂粉以及3.93g，98％的H₂SO₄和310cc的蒸馏水混合制备溶胶。用ZrO₂研磨剂研磨此混合物8小时以制作SiO₂/ZrO₂粉溶胶。A sol was prepared by mixing 152g of_SiO2 /_ZrO2 powder calcined at 1000°C with 15.2g of_SiO2 /_ZrO2 powder calcined at 500°C and 3.93g of 98%_H2SO4 and_310cc of distilled water. This mixture was ground for 8 hours with a ZrO₂ abrasive to make a SiO₂ /ZrO₂ powder sol.

将76mm宽的Fe/Cr/Al合金(Fe/20％Cr/5％Al)板带按人字型制成波纹状以形成1.20mm高的波纹和波峰到波峰2mn的间隔，并且人字型有20mm长的通道和6°的通道角，从而形成了每平方英寸有185穴的整体结构件。该板在900℃空气中热处理以形成粗糙的氧化物覆盖表面。A 76mm wide Fe/Cr/Al alloy (Fe/20%Cr/5%Al) strip is corrugated in a herringbone shape to form 1.20mm high corrugations and a peak-to-peak interval of 2mn, and the herringbone There are 20 mm long channels and a 6° channel angle, resulting in a monolithic structural member with 185 cavities per square inch. The panels were heat treated at 900°C in air to form a rough oxide-coated surface.

将SiO₂/ZrO₂溶胶喷涂在人字型波纹板的一侧并达到40微米厚，并且在950℃空气中焙烧该涂布板。Pd(NH₃)₂(NO₂)₂和Pt(NH₃)₂(NO₂)₂溶解在水和过量硝酸中以形成含有0.1g Pd/ml和Pd/Pt比值是6的溶液；将此溶液喷涂在涂SiO₂/ZrO₂的波纹上，最终形成的Pd载量为0.25g Pd/g.SiO₂/ZrO₂，然后在950℃空气中焙烧。SiO₂ /ZrO₂ sol was spray-coated on one side of the herringbone corrugated plate to a thickness of 40 μm, and the coated plate was fired at 950° C. in air. Pd(NH₃ )₂ (NO₂ )₂ and Pt(NH₃ )₂ (NO₂ )₂ were dissolved in water and excess nitric acid to form a solution containing 0.1 g Pd/ml and a Pd/Pt ratio of 6; The solution was sprayed on the SiO₂ /ZrO₂ -coated corrugations to a final Pd loading of 0.25 g Pd/g.SiO₂ /ZrO₂ , and then fired at 950°C in air.

对面折叠一条上述板使其有催化剂的一面面对着自己，卷此结构件以形成直径50mm的螺旋整体结构件。催化剂(卷成50mm直径的螺旋卷结构件)放入上述测试设备中。安置热电偶用以测量基质温度和催化剂下游气体温度。此外，水冷气体样品探头被安置在反应器中用以测量催化剂下游25cm处气体物流的组成。One of the above sheets was folded opposite so that the catalyst side faced itself, and the structure was rolled to form a helical monolithic structure with a diameter of 50mm. The catalyst (coiled into a 50 mm diameter spiral wound structure) was placed in the test apparatus described above. Thermocouples were placed to measure the substrate temperature and the gas temperature downstream of the catalyst. In addition, a water-cooled gas sample probe was placed in the reactor to measure the composition of the gas stream 25 cm downstream of the catalyst.

测试程序如下：The test procedure is as follows:

1.设定空气流率与气体透平空载情况一致。1. Set the air flow rate to be consistent with the no-load condition of the gas turbine.

2.设定空气温度值在气体透平空载循环时空气温度的范围内。2. Set the air temperature value within the range of the air temperature during the no-load cycle of the gas turbine.

3.增大燃料流率直到绝热燃烧温度为1200℃。3. Increase the fuel flow rate until the adiabatic combustion temperature is 1200°C.

4.增加空气温度以找到由催化剂过热决定的催化剂使用上限。在该测试过程中，催化剂使用温度上限是1050℃基质温度。4. Increase the air temperature to find the upper limit of catalyst use determined by catalyst overheating. During this test, the catalyst was used with an upper temperature limit of 1050°C substrate temperature.

5.类似地，减小空气温度直到找到催化剂使用下限温度，该温度是由排放物增加到超过规定值来决定的。在本测试过程中，当CO排放物在催化剂后25cm处超过5ppm(体积，干)时，入口气体温度作为下限温度。5. Similarly, reduce the air temperature until the lower catalyst operating temperature is found, which is determined by the increase in emissions above the specified value. During this test, the inlet gas temperature was used as the lower limit temperature when CO emissions exceeded 5 ppm (volume, dry) at 25 cm behind the catalyst.

6.在气体透平满载运转的通常空气流量下，重复步骤1到5。6. Repeat steps 1 through 5 at the normal air flow of the gas turbine at full load.

Indolene Clear规格汽油做为燃料。这是符合排放物标准的标准常规无铅气油。燃料通过喷嘴被注入到加热空气的主体流动物流中并在经过静态混合器前汽化以在催化剂进口形成均匀的燃料/空气混合物。燃料和空气物流被连续地实时测量，并且由自动反馈系统控制。Indolene Clear gasoline is used as fuel. This is standard conventional unleaded gas oil that meets emissions standards. Fuel is injected through nozzles into the main flow stream of heated air and vaporized before passing through a static mixer to form a homogeneous fuel/air mixture at the catalyst inlet. Fuel and air flows are continuously measured in real time and controlled by an automatic feedback system.

此催化剂结构件的测试结果和检试所用条件如下表1所示：The test result of this catalyst structure and the conditions used for inspection are shown in table 1 below:

                            表1   条件 空气流率  压力 Tad(℃) 在最佳范围时的入口温度 (SLPM)  (atm)   底部(℃)   顶部(℃)   空载   291   1.3   1150     230     400   1200     220     260   1250     220     220   满载   2127   2.9   1200     540     ＞620   1300     420     570总结：空载条件下，入口温度在230到400℃范围内，催化剂在等价于绝热燃烧温度1150℃的F/A比值下操作。在Tad为1200℃下，入口温度范围缩小到220～260℃，在1250℃下，催化剂不过热将不能操作。Table 1 condition air flow rate pressure Tad(°C) Inlet temperature in optimum range (SLPM) (atm) Bottom(°C) Top (°C) no load 291 1.3 1150 230 400 1200 220 260 1250 220 220 fully loaded 2127 2.9 1200 540 >620 1300 420 570 Summary: Under no-load conditions, the catalyst operates at an F/A ratio equivalent to an adiabatic combustion temperature of 1150°C at inlet temperatures ranging from 230 to 400°C. At a Tad of 1200°C, the inlet temperature range narrows to 220-260°C, and at 1250°C, the catalyst cannot be operated without overheating.

满载条件下，催化剂系统在540到＞620℃，Tad是1200℃和420到570℃，Tad是1300℃的使用范围内均使用得相当好。Under full load conditions, the catalyst system performed reasonably well in the service ranges of 540 to >620°C with a Tad of 1200°C and 420 to 570°C with a Tad of 1300°C.

此催化剂系统在空载下不具有宽的操作范围，并且不能用于必须从空载到满载情况下使用的透平，除非燃料/空气比值被控制在很窄的范围内。This catalyst system does not have a wide operating range at no load and cannot be used in turbines that must be operated from no load to full load unless the fuel/air ratio is controlled within a narrow range.

                      实施例2Example 2

为将低空气流率下非催化通道中燃料的燃烧降到最低，用与实施例1中同样的燃料评价图4所示的催化剂结构件。直线波纹通道具有1.65mm高的波纹和波峰到波峰间隔3.90mm的近似三角形状。人字型波纹板与实施例1中描述的类似，不同之处在于两块板高分别是0.76mm和0.91mm，波峰到波峰间隔分别是1.84和2.45。催化涂层(Pd-Pt/SiO₂/ZrO₂)的制备和涂布实施例1中所述。用实施例1中描述的同样方法测试此催化剂结构件的性能，结果见表2：The catalyst structure shown in Figure 4 was evaluated with the same fuel as in Example 1 in order to minimize fuel combustion in the non-catalyzed channels at low air flow rates. The straight corrugated channel has corrugations 1.65 mm high and an approximately triangular shape with a peak-to-peak spacing of 3.90 mm. The herringbone corrugated boards were similar to those described in Example 1, except that the heights of the two boards were 0.76 mm and 0.91 mm, respectively, and the peak-to-peak spacings were 1.84 and 2.45, respectively. The preparation and coating of the catalytic coating (Pd-Pt/SiO₂ /ZrO₂ ) is described in Example 1. Test the performance of this catalyst structure with the same method described in embodiment 1, the results are shown in Table 2:

                             表2   条件 空气流率  压力 Tad(℃) 在最佳范围时的入口温度 (SLPM)  (atm)   底部(℃)   顶部(℃)   空载   291   1.3   1200     460     ＞500   1300     290     550   满载   2127   2.9   1200     610     ＞620   1300     510     610总结：空载下此结构件比实施例1中的结构件性能好得多。在很低的空气流率下，催化剂基质不易过热。然而，满载下的操作范围下降，并且此结构件不能提供优化性能所需的在1200和1300℃Tad下的入口温度操作范围。明显地，使用开放的、大的非催化通道使催化剂在非常低质量流速下能更好操作，但是，此特定设计有些抑制催化通道和非催化通道之间的换热。这导致在高质量流率下离开催化剂的出口气体温度低和在满载条件下不能获得优化性能。Table 2 condition air flow rate pressure Tad(°C) Inlet temperature in optimum range (SLPM) (atm) Bottom(°C) Top (°C) no load 291 1.3 1200 460 >500 1300 290 550 fully loaded 2127 2.9 1200 610 >620 1300 510 610 Summary: The performance of this structural member under no load is much better than that of the structural member in Example 1. At very low air flow rates, the catalyst substrate is less prone to overheating. However, the operating range at full load is reduced and this structure does not provide the inlet temperature operating range of 1200 and 1300 °C Tad required for optimum performance. Clearly, the use of open, large non-catalytic channels allows the catalyst to operate better at very low mass flow rates, however, this particular design somewhat inhibits heat transfer between the catalytic and non-catalytic channels. This results in low outlet gas temperatures leaving the catalyst at high mass flow rates and inability to achieve optimal performance at full load conditions.

                      实施例3Example 3

图5的催化剂结构件用实施例1中描述的方法来制备和测试。在测试用催化剂结构件中，人字型波纹板与实施例1中描述的类似，除了两个人字波纹板的高分别为0.76mm和1.2mm，间隔分别为1.84和2.90，chevron角为6°，和直线峰形波纹板高1.63mm，波峰到波峰间隔4.52mm，平坦区域长度为3.7mm。催化剂是按实施例1制备的Pd-Pt/SiO₂/ZrO₂，并且按图5所示涂布。用Indolene Clear汽油进行实验，测试范围条件和结果在如下表3中显示：The catalyst structure of Figure 5 was prepared and tested using the method described in Example 1. In the test catalyst structure, the herringbone corrugated plates were similar to those described in Example 1, except that the heights of the two herringbone corrugated plates were 0.76mm and 1.2mm, the intervals were 1.84 and 2.90, and the chevron angle was 6° , and the straight peak-shaped corrugated plate is 1.63mm high, the peak-to-peak interval is 4.52mm, and the length of the flat area is 3.7mm. The catalyst was Pd-Pt/SiO₂ /ZrO₂ prepared as in Example 1 and coated as shown in FIG. 5 . Experiments were carried out with Indolene Clear gasoline, the test range conditions and results are shown in Table 3 below:

                             表3   条件 空气流率   压力  Tad(℃)    在最佳范围时的入口温度  (SLPM)  (atm)   底部(℃)   顶部(℃)   空载   291   1.3   1200     390     ＞500   1300     280     490   满载   2127   2.9   1200     570     ＞620   1300     470     620总结：该催化剂结构件在空载和满载条件下均有非常宽的操作范围。空载时，此催化剂可在入口温度160℃，1200℃Tad条件下和210℃1300℃Tad条件的范围内使用。满载时，此范围是＞50℃，1200℃Tad条件。这些操作范围是充分的Tad和在1200℃Tad下＞50℃，在1300℃Tad＞150℃。这些操作范围足以使该催化剂结构件适用于实际气体透平。与实施例1的常规技术比较表明实施例3的催化剂可在空载和满载条件下从1200到1300℃的Tad范围内使用。然而实施例1中的常规催化剂仅可在从1150℃到1200℃的Tad和空载时非常窄的催化剂入口温度范围内使用。此外，实施例1的常规技术需要将燃料/空气比控制在非常窄的范围内，这可能是非常困难的和昂贵的。实施例3的技术有非常广泛的使用范围，并且更易在实际中应用。在满载时，实施例3催化剂的使用范围几乎与实施例1催化剂一样宽。table 3 condition air flow rate pressure Tad(°C) Inlet temperature in optimum range (SLPM) (atm) Bottom(°C) Top (°C) no load 291 1.3 1200 390 >500 1300 280 490 fully loaded 2127 2.9 1200 570 >620 1300 470 620 Summary: The catalyst structure has a very wide operating range under both no-load and full-load conditions. When unloaded, this catalyst can be used in the range of inlet temperature 160°C, 1200°C Tad condition and 210°C 1300°C Tad condition. At full load, this range is >50°C, 1200°C Tad condition. These operating ranges are full Tad and >50°C at 1200°C Tad and >150°C at 1300°C Tad. These operating ranges are sufficient to make the catalyst structure suitable for use in practical gas turbines. Conventional technology comparison with Example 1 shows that the catalyst of Example 3 can be used in the Tad range from 1200 to 1300°C under no-load and full-load conditions. However the conventional catalyst in Example 1 can only be used over a very narrow catalyst inlet temperature range from 1150°C to 1200°C Tad and empty. Furthermore, the conventional technique of Example 1 requires controlling the fuel/air ratio within a very narrow range, which can be very difficult and expensive. The technology of embodiment 3 has a very wide application range, and is easier to apply in practice. At full load, the catalyst of Example 3 was used almost as broadly as the catalyst of Example 1.

本发明已通过一般描述和实施例说明。实施例不希望以任何方式限制在后面的权利要求书中定义的发明。它们仅仅是示例性的，此外，本领域技术人员可发现等价的方式实现这些权利要求中描述的发明。这些等价被认为是在权利要求发明的精神内。The invention has been illustrated by the general description and the examples. The examples are not intended to limit the invention defined in the following claims in any way. They are merely exemplary, and a person skilled in the art may find equivalent ways of practicing the invention described in these claims. Such equivalents are considered to be within the spirit of the claimed invention.

Claims (74)

1. catalyst structure, comprise a kind of heat-resisting supporting element material of forming by a plurality of common walls, the vertical passage that these walls form a series of adjacent layouts flows through for a kind of mobile gas reaction mixture, wherein at least a portion internal surface of at least a portion passage scribbles catalyzer, the internal surface of remaining passage is not coated with catalyzer, and the flow passage ratio of using for reaction mixture that the internal surface of the internal surface that is coated with catalyst channels like this and the passage of adjacent catalyst-free forms heat exchange relationship and is coated with wherein that the catalyst channels structure forms is more tortuous by the flow passage that the passage of catalyst-free forms.

2. the catalyst structure of claim 1, wherein be coated with the variation of catalyst channels by cross section, along the variation of the y direction of passage or cross section and along they y direction variation combination and periodically change, so that change at a plurality of at least points when gas reaction mixture flows through the flow direction that is being coated with at least a portion gas reaction mixture in the catalyst channels when being coated with catalyst channels, and the passage of catalyst-free is essentially straight and variation that do not have cross section along its y direction, the feasible essentially no variation of flow direction of flowing through the gas reaction mixture of catalyst-free passage.

3. the catalyst structure of claim 2, the passage that wherein is coated with catalyzer is by be coated with that the wall of catalyzer repeats inside or outwardly-bent of the Y passage along passage or by using baffle plate, deflection plate or other obstacle placed along a plurality of positions of passage Y to change cross section partly to hinder the flow direction of gas reaction mixture.

4. the catalyst structure of claim 3, the variation that wherein is coated with the cross section of catalyst channels is inside and outwardly-bent realization by the repetition of the wall that is coated with catalyst channels, and catalyst channels finishes and the chevron shaped ripple that this bending is to use the stacked corrugated sheet of unnested version to form is coated with.

5. the catalyst structure of claim 4, the three-decker that wherein is coated with catalyst channels and catalyst-free path and is by a repetition forms, this three-decker comprises the first layer of a corrugated sheet, this corrugated sheet has the vertical peak that is separated by the flat region, these flat regions are stacked in a second layer of being made up of corrugated sheet, wherein ripple forms adjacent vertical peak and paddy, these peaks and paddy form chevron shaped to constitute the second layer along plate length, the second layer is stacked in the 3rd layer that is made up of wavy metal plate with non-nested mode, wherein ripple forms vertical peak and paddy, these peaks and paddy form chevron shaped to constitute the 3rd layer along plate length, with be coated with the top of the bottom of first layer and the 3rd layer so that when the first layer of repetitive structure places the 3rd layer of below that next adjacent stacked type repeats three-decker, form the catalyst-free passage with reaction mixture with catalyzer, and be coated with catalyst channels and forming between the top of the bottom of the first layer that repeats three-decker and the second layer and between the top the bottom of the second layer and the 3rd layer.

6. catalyst structure, comprise a kind of heat-resisting supporting element material of forming by a plurality of common walls, the vertical passage that these walls form a series of adjacent layouts flows through for a kind of gas reaction mixture, wherein at least a portion internal surface of at least a portion passage scribbles catalyzer, the internal surface of remaining passage is not coated with catalyzer, the internal surface that is coated with catalyst channels like this with the internal surface formation heat exchange relationship of the passage of adjacent catalyst-free and wherein:

(a) passage that is coated with catalyzer has littler average hydraulic diameter (D than catalyst-free passage_h);

(b) passage that is coated with catalyzer has higher film heat transfer coefficient (h) than catalyst-free passage; With

(c) it is more tortuous than the flow path that catalyst-free passage forms to be coated with the flow path that catalyst channels forms.

7. the catalyst structure of claim 6 wherein is coated with the average D of catalyst channels_hAverage D with the catalyst-free passage_hNumeric ratio between 0.15 to 0.9.

8. the catalyst structure of claim 7 wherein is coated with the average D of catalyst channels_hAverage D with the catalyst-free passage_hNumeric ratio between 0.3 to 0.8.

9. the catalyst structure of claim 6, the ratio (h (cat)/h (non-cat)) of film heat transfer coefficient (h) that wherein is coated with the film heat transfer coefficient (h) of the passage of catalyzer and catalyst-free passage is between 1.1 to 7.

10. the catalyst structure of claim 9, wherein (h (cat)/h (non-cat)) is between 1.3 to 4.

11. the catalyst structure of claim 6, the ratio that wherein is coated with general passage volume in heat transfer surface area and the structural member between catalyst channels and the catalyst-free passage is greater than 0.5mm^-1

12. the catalyst structure of claim 11, the ratio that wherein is coated with general passage volume in heat transfer surface area and the structural member between catalyst channels and the catalyst-free passage is 0.5 to 2mm^-1In the scope.

13. the catalyst structure of claim 12, the ratio that wherein is coated with general passage volume in heat transfer surface area and the structural member between catalyst channels and the catalyst-free passage is 0.5 to 1.5mm^-1In the scope.

14. claim 11,12 or 13 catalyst structure, wherein h (cat)/h (non-cat) is between about 1.1 to about 7 and be coated with the average D of catalyst channels_hAnd the ratio of the average Dh of catalyst-free passage is between 0.15 to 0.9

15. claim 11,12 or 13 catalyst structure, wherein h (cat)/h (non-cat) is between about 1.3 to about 4 and be coated with the average D of catalyst channels_hWith the average D of catalyst-free passage_hRatio between 0.3 to 0.8

16. catalyst structure, comprise a kind of heat-resisting supporting element material of forming by a plurality of common walls, the vertical passage that these walls form a series of adjacent layouts flows through for a kind of gas reaction mixture, wherein at least a portion internal surface of at least a portion passage scribbles catalyzer, the internal surface of remaining passage is not coated with catalyzer, the film that the internal surface that is coated with the passage of the internal surface of catalyst channels and adjacent catalyst-free like this forms heat exchange relationship and wherein the is coated with catalyst channels system (h) of conducting heat is more than 1.5 times of catalyst-free channel membrane heat-transfer coefficient h, and being coated with catalyst channels, to account for 20% to 80% and the flow passage of using for reaction mixture that is coated with that catalyst channels forms of total open front area in the catalyst structure more tortuous than the flow passage of catalyst-free passage formation.

17. the catalyst structure of claim 16 wherein is coated with between the ratio 1.5 and 7 of h of the h of catalyst channels and catalyst-free passage.

18. catalyst structure, comprise a kind of heat-resisting supporting element material of forming by a plurality of common walls, the vertical passage that these walls form a series of adjacent layouts flows through for a kind of gas reaction mixture, wherein at least a portion internal surface of at least a portion passage scribbles catalyzer, the internal surface of remaining passage is not coated with catalyzer, the internal surface formation heat exchange relationship of the internal surface that is coated with catalyst channels like this and the passage of adjacent catalyst-free and wherein be coated with the average hydraulic diameter (D of catalyzer_h) little than catalyst-free passage, be coated with the average D of catalyst channels_hAverage D with the catalyst-free passage_hRatio less than the ratio of the open front area that is coated with catalyzer with the open front area of catalyst-free passage.

19. the catalyst structure of claim 18, the open front area that wherein is coated with catalyst channels account for 20% to 80% of total open front area in the catalyst structure.

20. comparing with number, the catalyst structure of claim 1 or 6, the size that wherein is coated with catalyst channels and the number and the size of catalyst-free passage make channel volume that 35% to 70% reaction mixture can flow through in being coated with catalyst channels.

21. the catalyst structure of claim 20, the channel volume that wherein about 50% reaction mixture can flow through is in being coated with catalyst channels.

22. catalyst structure, comprise a kind of heat-resisting supporting element material of forming by a plurality of common walls, the vertical passage that these walls form a series of adjacent layouts flows through for a kind of gas reaction mixture, wherein at least a portion internal surface of at least a portion passage scribbles catalyzer, the internal surface of remaining passage is not coated with catalyzer, the internal surface that is coated with catalyst channels like this with the internal surface formation heat exchange relationship of the passage of adjacent catalyst-free and wherein:

(a) be coated with catalyst channels and higher film heat transfer coefficient (h) arranged than catalyst-free passage;

(b) be coated with catalyst channels and littler average hydraulic diameter (D arranged than catalyst-free passage_h); With

(c) be coated with the average D of catalyst channels_hAverage D with the catalyst-free passage_hRatio less than the ratio of the open front area that is coated with catalyst channels with catalyst-free passage open front area.

23. the catalyst structure of claim 22 wherein is coated with the average D of catalyst channels_hAverage D with the catalyst-free passage_hRatio between 0.15 and 0.9.

24. the catalyst structure of claim 23 wherein is coated with the average D of catalyst channels_hAverage D with the catalyst-free passage_hRatio between 0.3 and 0.8.

25. the catalyst structure of claim 22, the ratio (h (cat)/h (non-cat)) of film heat transfer coefficient (h) that wherein is coated with the film heat transfer coefficient (h) of catalyst channels and catalyst-free passage is between 1.1 and 7.

26. the catalyst structure of claim 25, wherein h (cat)/h (non-cat) is between 1.3 and 4.

27. the catalyst structure of claim 22, the ratio that wherein is coated with general passage volume in heat transfer surface area and the structural member between catalyst channels and the catalyst-free passage is greater than 0.5mm^-1

28. the catalyst structure of claim 27, the ratio that wherein is coated with general passage volume in heat transfer surface area and the structural member between catalyst channels and the catalyst-free passage is 0.5 to 2mm^-1In the scope.

29. the catalyst structure of claim 28, the ratio that wherein is coated with general passage volume in heat transfer surface area and the structural member between catalyst channels and the catalyst-free passage is 0.5 to 1.5mm^-1In the scope.

30. the catalyst structure of claim 27,28 or 29, wherein h (cat)/h (non-cat) is between 1.1 to 7 and be coated with the average D of catalyst channels_hWith the average D of catalyst-free passage_hRatio between 0.15 to 0.9

31. the catalyst structure of claim 27,28 or 29, wherein h (cat)/h (non-cat) is between 1.3 to 4 and be coated with the average D of catalyst channels_hWith the average D of catalyst-free passage_hRatio between 0.3 to 0.8

32. comparing with number, the catalyst structure of claim 22 or 27, the size that wherein is coated with catalyst channels and the number and the size of catalyst-free passage make channel volume that 35% to 70% reaction mixture can flow through in being coated with catalyst channels.

33. the catalyst structure of claim 32, the channel volume that wherein about 50% reaction mixture can flow through is in being coated with catalyst channels.

34. catalyst structure, comprise a kind of heat-resisting supporting element material of forming by a plurality of common walls, the vertical passage that these walls form a series of adjacent layouts flows through for a kind of gas reaction mixture, wherein at least a portion internal surface of at least a portion passage scribbles catalyzer, the internal surface of remaining passage is not coated with catalyzer, the internal surface that is coated with catalyst channels like this with the internal surface formation heat exchange relationship of the passage of adjacent catalyst-free and wherein:

(a) be coated with catalyst channels and higher film heat transfer coefficient (h) arranged than catalyst-free passage;

(b) flow through greater than 50% complete reaction mixture and be coated with catalyst channels; With

(c) flow passage of using for reaction mixture that is coated with that catalyst channels forms is more tortuous than the flow passage that catalyst-free passage forms.

35. catalyst structure, comprise a kind of heat-resisting supporting element material of forming by a plurality of common walls, the vertical passage that these walls form a series of adjacent layouts flows through for a kind of gas reaction mixture, wherein at least a portion internal surface of at least a portion passage scribbles catalyzer, the internal surface of remaining passage is not coated with catalyzer, the internal surface that is coated with catalyst channels like this with the internal surface formation heat exchange relationship of the passage of adjacent catalyst-free and wherein:

(a) film heat transfer coefficient (h) that is coated with catalyst channels is more than 1.2 times of catalyst-free passage;

(b) flow through greater than 40% but less than 50% complete reaction mixture and be coated with catalyst channels; With

(c) flow passage of using for reaction mixture that is coated with that catalyst channels forms is more tortuous than the flow passage that catalyst-free passage forms.

36. catalyst structure, comprise a kind of heat-resisting supporting element material of forming by a plurality of common walls, the vertical passage that these walls form a series of adjacent layouts flows through for a kind of gas reaction mixture, wherein at least a portion internal surface of at least a portion passage scribbles catalyzer, the internal surface of remaining passage is not coated with catalyzer, the internal surface that is coated with catalyst channels like this with the internal surface formation heat exchange relationship of the passage of adjacent catalyst-free and wherein:

(a) film heat transfer coefficient (h) that is coated with catalyst channels is more than 1.3 times of catalyst-free passage;

(b) greater than 30% but flow through surplus catalyst channels less than 40% complete reaction mixture; With

(c) flow passage of using for reaction mixture that is coated with that catalyst channels forms is more tortuous than the flow passage that catalyst-free passage forms.

37. catalyst structure, comprise a kind of heat-resisting supporting element material of forming by a plurality of common walls, the vertical passage that these walls form a series of adjacent layouts flows through for a kind of gas reaction mixture, wherein at least a portion internal surface of at least a portion passage scribbles catalyzer, the internal surface of remaining passage is not coated with catalyzer, the internal surface that is coated with catalyst channels like this with the internal surface formation heat exchange relationship of the passage of adjacent catalyst-free and wherein:

(a) film heat transfer coefficient (h) that is coated with the passage of catalyzer is more than 1.5 times of catalyst-free passage;

(b) flow through greater than 20% but less than 30% complete reaction mixture and be coated with catalyst channels; With

(c) flow passage of using for reaction mixture that is coated with that catalyst channels forms is more tortuous than the flow passage that catalyst-free passage forms.

38. catalyst structure, comprise a kind of heat-resisting supporting element material of forming by a plurality of common walls, the vertical passage that these walls form a series of adjacent layouts flows through for a kind of gas reaction mixture, wherein at least a portion internal surface of at least a portion passage scribbles catalyzer, the internal surface of remaining passage is not coated with catalyzer, the internal surface that is coated with catalyst channels like this with the internal surface formation heat exchange relationship of the passage of adjacent catalyst-free and wherein:

(a) film heat transfer coefficient (h) that is coated with the passage of catalyzer is more than 2.0 times of catalyst-free passage;

(b) flow through greater than 10% but less than 20% complete reaction mixture and be coated with catalyst channels; With

(c) flow passage of using for reaction mixture that is coated with that catalyst channels forms is more tortuous than the flow passage that catalyst-free passage forms.

39. claim 34,35,36,37 or 38 catalyst structure, wherein being coated with catalyst channels has the average hydraulic diameter (D littler than the passage of catalyst-free_h).

40. catalyst structure, comprise a kind of heat-resisting supporting element material of forming by a plurality of common walls, the vertical passage that these walls form a series of adjacent layouts flows through for a kind of ignition mixture, wherein at least a portion internal surface of at least a portion passage scribbles catalyzer, the internal surface of remaining passage is not coated with catalyzer, the internal surface that is coated with catalyst channels like this with the internal surface formation heat exchange relationship of the passage of adjacent catalyst-free and wherein:

(a) be coated with catalyst channels the film heat transfer coefficient higher than catalyst-free passage (h) arranged;

(b) be coated with catalyst channels the average hydraulic diameter (D littler than catalyst-free passage arranged_h); With

(c) be coated with more tortuous than the flow passage that catalyst-free passage forms that catalyst channels forms for the ignition mixture flow passage.

41. catalyst structure, comprise a kind of heat-resisting supporting element material of forming by a plurality of common walls, the vertical passage that these walls form a series of adjacent layouts flows through for a kind of ignition mixture, wherein at least a portion internal surface of at least a portion passage scribbles catalyzer, the internal surface of remaining passage is not coated with catalyzer, the internal surface that is coated with catalyst channels like this with the internal surface formation heat exchange relationship of the passage of adjacent catalyst-free and wherein:

(a) be coated with catalyst channels the film heat transfer coefficient higher than catalyst-free passage (h) arranged;

(b) be coated with catalyst channels the average hydraulic diameter (D littler than catalyst-free passage arranged_h); With

(c) be coated with the average D of catalyst channels_hAverage D with the catalyst-free passage_hRatio less than the ratio of the open front area that is coated with catalyst channels with catalyst-free passage open front area.

42. the catalyst structure of claim 40 or 41, wherein whole ignition mixtures of 35% to 70% flow through and are coated with catalyst channels.

43. the catalyst structure of claim 40 or 41, whole ignition mixtures of wherein about 50% flow through and are coated with catalyst channels.

44. the catalyst structure of claim 40 or 41, the ratio that wherein is coated with general passage volume in heat transfer surface area and the structural member between catalyst channels and the catalyst-free passage is greater than 0.5mm^-1

45. the catalyst structure of claim 44 wherein is coated with the average D of catalyst channels_hAverage D with the catalyst-free passage_hNumeric ratio between 0.15 to 0.9.

46. the catalyst structure of claim 45 wherein is coated with the average D of catalyst channels_hAverage D with the catalyst-free passage_hNumeric ratio between 0.3 to 0.8.

47. the catalyst structure of claim 45, the ratio (h (cat)/h (non-cat)) of film heat transfer coefficient (h) that wherein is coated with the film heat transfer coefficient (h) of the passage of catalyzer and catalyst-free passage is between 1.1 to 7.

48. the catalyst structure of claim 46, the ratio (h (cat)/h (non-cat)) of film heat transfer coefficient (h) that wherein is coated with the film heat transfer coefficient (h) of the passage of catalyzer and catalyst-free passage is between 1.3 to 4.

49. the catalyst structure of claim 42, wherein the supporting element material is selected from stupalith, heat-resistant inorganic oxide, intermetallic compounds material, carbide, nitride and metallic material.

50. the catalyst structure of claim 49, wherein inorganic oxide is selected from silica, magnesium oxide, aluminium oxide, titanium oxide, zirconium oxide and their mixture, and metallic material is selected from aluminium, the refractory metal alloy, and stainless steel contains aluminum steel and aluminium-containing alloy.

51. the catalyst structure of claim 49, wherein catalyzer is one or more platinum group elementss.

52. the catalyst structure of claim 51, wherein catalyzer comprises the mixture of palladium or palladium and platinum.

53. the catalyst structure of claim 51, wherein the supporting element material thereon at least a portion also comprise the basic unit of a kind of zirconium oxide, titanium oxide, aluminium oxide, silica or other refractory metal oxides.

54. the catalyst structure of claim 53, wherein basic unit comprises the mixture of aluminium oxide, silica or aluminium oxide and silica.

55. the catalyst structure of claim 53, wherein basic unit comprises zirconium oxide.

56. the catalyst structure of claim 53, wherein catalyzer is the palladium in basic unit or the mixture of palladium and platinum.

57. the combustion method of an ignition mixture comprises the following steps:

(a) fuel and oxygen-containing gas are mixed to form ignition mixture;

(b) mixture is contacted with a kind of heat resistant catalyst supporting element material of being made up of a plurality of common walls, the vertical passage that these walls form a series of adjacent layouts flows through for a kind of ignition mixture, wherein at least a portion internal surface of at least a portion passage scribbles catalyzer, the internal surface of remaining passage is not coated with catalyzer, the internal surface that is coated with catalyst channels like this with the internal surface formation heat exchange relationship of the passage of adjacent catalyst-free and wherein:

(i) be coated with catalyst channels the film heat transfer coefficient higher than catalyst-free passage (h) arranged;

(ii) be coated with catalyst channels the average hydraulic diameter (D littler than catalyst-free passage arranged_h); With

(iii) be coated with more tortuous than the flow path that catalyst-free passage forms that catalyst channels forms for the ignition mixture flow path.

58. the combustion method of an ignition mixture comprises the following steps:

(a) fuel and oxygen-containing gas are mixed to form ignition mixture;

(b) mixture is contacted with a kind of heat resistant catalyst supporting element material of being made up of a plurality of common walls, the vertical passage that these walls form a series of adjacent layouts flows through for a kind of ignition mixture, wherein at least a portion internal surface of at least a portion passage is coated with the catalyzer that is useful on the oxidation ignition mixture, the internal surface of remaining passage is not coated with catalyzer, the internal surface that is coated with catalyst channels like this with the internal surface formation heat exchange relationship of the passage of adjacent catalyst-free and wherein:

(i) be coated with catalyst channels the film heat transfer coefficient higher than catalyst-free passage (h) arranged;

(ii) be coated with catalyst channels the average hydraulic diameter (D littler than catalyst-free passage arranged_h); With

(iii) be coated with the average D of catalyst channels_hAverage D with the catalyst-free passage_hRatio less than the ratio of the open front area that is coated with catalyst channels with catalyst-free passage open front area.

59. the method for claim 57 or 58, the ratio that wherein is coated with general passage volume in heat transfer surface area and the structural member between catalyst channels and the catalyst-free passage is greater than 0.5mm^-1

60. the method for claim 59, the distribution of wherein flowing through the ignition mixture of catalyst support member makes 35% to 70% ignition mixture flow through the passage that is coated with catalyzer.

61. the method for claim 60, wherein about 50% ignition mixture flow through and are coated with catalyst channels.

62. the method for claim 57 or 58, wherein catalyst support member comprises stupalith, heat-resistant inorganic oxide, intermetallic compounds material, carbide, nitride or metallic material.

63. the method for claim 62, wherein catalyst support member comprises metallic material, is selected from aluminium, high-temperature alloy, stainless steel, aluminium-containing alloy and contains the ferro-alloy of aluminium.

64. the method for claim 63, wherein catalyst support member comprises iron or the nonferrous alloy that contains aluminium.

65. the method for claim 64, wherein catalyst support member thereon at least a portion also comprise the basic unit of a kind of zirconium oxide, titanium oxide, aluminium oxide, silica or refractory metal oxides.

66. the method for claim 65, wherein the catalyst metals supporting element thereon at least a portion also comprise a kind of zirconium oxide basic unit.

67. the method for claim 66, wherein catalyst material is one or more platinum group elementss.

68. the method for claim 67, wherein catalyst material comprises palladium.

69. the method for claim 68, wherein the theoretical adiabatic combustion temperature of catalyzer ignition mixture is greater than 900 ℃.

70. the method for claim 57 or 58, wherein ignition mixture partial combustion when contacting, perfect combustion in the homogeneous combustion district after ignition mixture flows through catalyst structure with catalyst structure.

71. comparing with number, the catalyst structure of claim 14, the size that wherein is coated with catalyst channels and the number and the size of catalyst-free passage make channel volume that 35% to 70% reaction mixture can flow through in being coated with catalyst channels.

72. comparing with number, the structural member of the catalyzer of claim 15, the size that wherein is coated with catalyst channels and the number and the size of catalyst-free passage make channel volume that 35% to 70% reaction mixture can flow through in being coated with catalyst channels.

73. the method for claim 59, wherein catalyst support member comprises stupalith, heat-resistant inorganic oxide, intermetallic compounds material, carbide, nitride or metallic material.

74. the method for claim 60, wherein catalyst support member comprises stupalith, heat-resistant inorganic oxide, intermetallic compounds material, carbide, nitride or metallic material.

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